Transition metal complexes, their preparation and use

ABSTRACT

Novel transition metal complexes are provided which represent viable catalysts for a broad variety of reactions such as hydrogenation reactions and metathesis reactions. Novel preparation processes are made available via unprecedented routes inter alia not involving structures according to Grubbs I or Grubbs II catalysts.

FIELD OF THE INVENTION

The present invention relates to novel transition metal complexes aswell as novel transition metal complex catalysts, their preparation andtheir use, in particular for metathesis or hydrogenation reactions.

BACKGROUND OF THE INVENTION

Metathesis reactions are used widely in chemical syntheses, e.g. in theform of ring-closing metatheses (RCM), cross metatheses (CM),ring-opening metatheses (ROM), ring-opening metathesis polymerizations(ROMP), cyclic diene metathesis polymerizations (ADMET),self-metathesis, reaction of alkenes with alkynes (enyne reactions),polymerization of alkynes and olefinization of carbonyls. Metathesisreactions are employed, for example, for the synthesis of olefins, forring-opening polymerization of norbornene derivatives, for thedepolymerisation of unsaturated polymers and for the synthesis oftelechelic polymers.

A broad variety of metathesis catalysts are known, inter alia, fromWO-A-96/04289 and WO-A-97/06185. They often have the following generalstructure:

where M is osmium or ruthenium, the radicals R are identical ordifferent organic radicals having a great structural variety, X¹ and X²are anionic ligands and the ligands L are uncharged electron-donors. Inthe literature, the term “anionic ligands” in the context of suchmetathesis catalysts always refers to ligands which, when being viewedseparately from the metal centre, are negatively charged for a closedelectron shell.

In the meantime it has been shown that certain transition metalcomplexes also show catalytic activity in hydrogenation reactions ofvarious substrates.

Well-known metathesis catalysts are for example the so-called Grubbscatalysts like Grubbs I and Grubbs II catalysts.

A lot of different catalysts have been developed and mostly thesynthesis of such catalysts involves as one precursor the abovementioned Grubbs I or II catalysts.

In various publications ester hydrogenation catalysts are disclosedwhich all possess tridentate amino-phosphine ligands. Their preparation,however, is often extremely costly. Angew. Chem. Int. Ed. 2013, 52, 1-6discloses the hydrogenation of low molecular weight carboxylic acidesters using different complex catalysts containing tridentate“SNS”-ligands as those shown in the following:

In Organometallics 2007, 26, 5803-5814 ruthenium alkylidene complexes ofchelating amine ligands are disclosed. In particular two bidentateamino-benzyloxy ligands and two tridentate amino-bis(benzyloxy) ligandswere prepared as well as ruthenium complexes containing such ligands asshown in the following scheme:

In Organometallics 2007, 26, 5803-5814 it is reported that the twocatalysts bearing the tridentate [ONO] ligand display low thermalstability and low catalytic activity in RCM of diethylallylmalonate,i.e. a reasonably high conversion can be achieved only at very longreaction times (see Table 3). On the other hand Table 3 of the referenceshows that metathesis activity of such catalysts increases upon additionof a Bronsted acid like HCl or H₂SO₄, however at the expense of anincreased decomposition rate of the catalyst showing that the catalystsare less robust than desired.

In Organometallics 2005, 24, 4289-4297 Ruthenium based carbene complexesare disclosed which contain a bulky tridentate ligand, as e.g. theN,N′-bis(2,6-diisopropylphenyl)-2,6-pyridinedicarboxamide pincer ligandas [ONO] ligand. Such complexes are shown in the following scheme

In the ring closing metathesis of 1,7 octadiene to cyclohexene thetriphenylphosphine stabilized [ONO] catalyst (4a) only showed lowconversions. After 3 hours at 80° C. 76% product was observed as well as24% isomers. Only a prolonged reaction time of up to 27 hours yieldedconversion up to 98%. The presence of proton sources, i.e. Bronstedacids did not shown any influence on the catalyst activity whileactivation with Lewis acids even reduced the product yield drasticallyalong with increased amounts of isomers.

Therefore, it was the object of the present invention to provide anactive and robust, novel catalyst for a broad variety of reactionsincluding metathesis and hydrogenation reactions. In particular thecatalysts should not undergo a substantial decomposition under thereaction conditions and also provide acceptable conversions inreasonable reaction times compared to the slow reactions known fromprior art for catalysts containing tridentate ligands.

SUMMARY OF THE INVENTION

Surprisingly novel transition metal complexes having general formula (I)could be provided

wherein

-   M means Ru, Os or Fe;-   X means O or S;-   D means S, O, PR², or NR² with R² meaning straight chain or branched    C₁-C₁₄ alkyl, preferably straight chain or branched C₁-C₆ alkyl,    C₃-C₈ cycloalkyl, preferably C₃-C₆ cycloalkyl, C₆-C₂₄ aryl,    preferably phenyl;-   Y means a divalent moiety, preferably unsubstituted or substituted    C₂-C₆ alkylene, preferably 1,2-ethylene, 1,3-propylene, or    1,4-butylene, or a unsubstituted or substituted C₆-C₁₀ arylene    group, preferably 1,2-phenylene or 2,3-napthylene;-   R means unsubstituted or substituted C₆-C₁₄, preferably C₆-C₁₀ aryl,    more preferably phenyl with none, 1, 2, 3, 4, or 5 substituents    selected from the group consisting of F, Cl, Br, and I;-   L¹ means a ligand, preferably P(R²)₃ wherein R² means unsubstituted    or substituted, straight chain or branched C₁-C₁₄ alkyl,    unsubstituted or substituted C₆-C₂₄ aryl, or unsubstituted or    substituted C₃-C₂₀ cycloalkyl or an N-heterocyclic carbene ligand;-   Z means B, Al, Ga, or In, preferably B;-   R¹ are identical or different and represent F, Cl, Br, I, preferably    Cl, unsubstituted or substituted, straight chain or branched C₁-C₁₄    alkyl, preferably C₁-C₆ alkyl, C₃-C₈ cycloalkyl, preferably C₅-C₆    cycloalkyl, unsubstituted or substituted C₆-C₂₄ aryl, preferably    phenyl;-   X¹ means F, Cl, Br, or I.-   L² is a two electron donor ligand, preferably CH₃CN, pyridine or    tetrahydrofurane; and n is either 0 or 1,-   Q is either P, B, Al, As, Ga or Sb, preferably P or B,-   R³ are identical or different and represent F, Cl, Br, I, preferably    F, unsubstituted or substituted, straight chain or branched C₁-C₁₄    alkyl, preferably C₁-C₆ alkyl, C₃-C₈ cycloalkyl, preferably C₅-C₆    cycloalkyl, unsubstituted or substituted C₆-C₂₄ aryl, preferably    phenyl or (C₆F₅), and-   m is 4, 5 or 6, preferably 4 or 6.

Such transition metal complexes are feasible and viable catalysts forcatalyzing different types of reactions, in particular metathesisreactions and hydrogenation reactions.

The invention further relates to a process for preparing the complexesaccording to general formula (I) comprising

-   (1) reacting the complex of general formula (II)

-   -   wherein    -   M means Ru, Os or Fe;    -   X means O or S;    -   D means S, O, PR², or NR² with R² meaning straight chain or        branched C₁-C₁₄ alkyl, preferably straight chain or branched        C₁-C₆ alkyl, C₃-C₈ cycloalkyl, preferably C₅-C₆ cycloalkyl,        C₆-C₂₄ aryl, preferably phenyl;    -   Y means a divalent moiety, preferably unsubstituted or        substituted C₂-C₆ alkylene, preferably 1,2-ethylene,        1,3-propylene, or 1,4-butylene, or a unsubstituted or        substituted C₆-C₁₀ arylene group, preferably 1,2-phenylene or        2,3-napthylene;    -   R means unsubstituted or substituted C₆-C₁₄, preferably C₆-C₁₀        aryl, more preferably phenyl with none, 1, 2, 3, 4, or 5        substituents selected from the group consisting of F, Cl, Br,        and I;    -   L¹ means a ligand, preferably P(R²)₃ wherein R² means        unsubstituted or substituted, straight chain or branched C₁-C₁₄        alkyl, unsubstituted or substituted C₆-C₂₄ aryl, or        unsubstituted or substituted C₃-C₂₀ cycloalkyl or an        N-heterocyclic carbene ligand;    -   with a compound of general formula (III)        ZX¹(R¹)₂  (III)    -   wherein    -   Z means B, Al, Ga or In, preferably B;    -   X¹ means F, Cl, Br, or I; preferably Cl; and    -   R¹ are identical or different and represent F, Cl, Br, I,        preferably Cl, unsubstituted or substituted, straight chain or        branched C₁-C₁₄—, preferably C₁-C₆ alkyl, C₃-C₈ cycloalkyl,        preferably C₅-C₆ cycloalkyl, unsubstituted or substituted C₆-C₂₄        aryl, preferably phenyl;    -   resulting in a complex according to general formula (IV)

-   -   wherein M, X, D, Y, R, X¹, and R¹ have the same meanings as        outlined above for general formulae (II) and (III), and    -   reacting the compound of general formula (IV) with a compound of        general formula (Va)        Z(R¹)₃  (Va)    -   wherein    -   Z means B, Al, Ga or In; preferably B, and    -   R¹ are identical or different and represent F, Cl, Br, I,        preferably Cl, unsubstituted or substituted, straight chain or        branched C₁-C₁₄—, preferably C₁-C₆ alkyl, C₃-C₈ cycloalkyl,        preferably C₅-C₆ cycloalkyl, unsubstituted or substituted C₆-C₂₄        aryl, preferably phenyl;    -   or    -   with a compound of general formula (Vb)        GQ(R³)_(m)  (Vb)    -   wherein    -   G is K, Na, Li, Cs, Ag or Cu, preferably K,    -   Q is either P, B, Al, As, Ga or Sb, preferably P or B,    -   R³ are identical or different and represent F, Cl, Br, I,        preferably F, unsubstituted or substituted, straight chain or        branched C₁-C₁₄ alkyl, preferably C₁-C₆ alkyl, C₃-C₈ cycloalkyl,        preferably C₅-C₆ cycloalkyl, unsubstituted or substituted C₆-C₂₄        aryl, preferably phenyl or (C₆F₅), and    -   m is 4, 5 or 6, preferably 4 or 6.    -   to obtain the complex catalyst according to general formula (I)        with n being 0 and

-   (2) optionally adding the ligand L² to obtain the complex catalyst    according to general formula (I) with n being 1, wherein such ligand    L² may be added simultaneously to the compound of general formula    (Va) or (Vb) in step 2 or thereafter.

The invention further relates to novel transition metal complexesaccording to general formula (IV)

wherein

-   M means Ru, Os or Fe;-   X means O or S;-   D means S, O, PR², or NR² with R² meaning straight chain or branched    C₁-C₁₄ alkyl, preferably straight chain or branched C₁-C₆ alkyl,    C₃-C₈ cycloalkyl, preferably C₅-C₆ cycloalkyl, C₆-C₂₄ aryl,    preferably phenyl;-   Y means a divalent moiety, preferably unsubstituted or substituted    C₂-C₆ alkylene, preferably 1,2-ethylene, 1,3-propylene, or    1,4-butylene, or a unsubstituted or substituted C₆-C₁₀ arylene    group, preferably 1,2-phenylene or 2,3-napthylene;-   R means unsubstituted or substituted C₆-C₁₄, preferably C₆-C₁₀ aryl,    more preferably phenyl with none, 1, 2, 3, 4, or 5 substituents    selected from the group consisting of F, Cl, Br, and I;-   L¹ means a ligand, preferably P(R²)₃ wherein R² means unsubstituted    or substituted, straight chain or branched C₁-C₁₄ alkyl,    unsubstituted or substituted C₆-C₂₄ aryl, or unsubstituted or    substituted C₃-C₂₀ cycloalkyl or an N-heterocyclic carbene ligand;-   Z means B, Al, Ga, or In, preferably B;-   R¹ are identical or different and represent F, Cl, Br, I, preferably    Cl, unsubstituted or substituted, straight chain or branched C₁-C₁₄    alkyl, preferably C₁-C₆ alkyl, C₃-C₈ cycloalkyl, preferably C₅-C₆    cycloalkyl, unsubstituted or substituted C₆-C₂₄ aryl, preferably    phenyl; and-   X¹ means F, Cl, Br, or I.

Such transition metal complexes according to general formula (IV) on theone hand are important intermediates in order to produce the inventivetransition metal complexes according to general formula (I) and on theother hand are also viable catalysts for certain reactions, inparticular hydrogenation reactions.

The invention further relates to novel transition metal complexesaccording to general formula (VI)

wherein

-   M means Ru, Os or Fe;-   X means O or S;-   D means S, O, or PR² with R² meaning straight chain or branched    C₁-C₁₄ alkyl, preferably straight chain or branched C₁-C₆ alkyl,    C₃-C₈ cycloalkyl, preferably C₅-C₆ cycloalkyl, C₆-C₂₄ aryl,    preferably phenyl;-   Y means a divalent moiety, preferably unsubstituted or substituted    C₂-C₆ alkylene, preferably 1,2-ethylene, 1,3-propylene, or    1,4-butylene, or a unsubstituted or substituted C₆-C₁₀ arylene    group, preferably 1,2-phenylene or 2,3-napthylene;-   R means unsubstituted or substituted C₆-C₁₄, preferably C₆-C₁₀ aryl,    more preferably phenyl with none, 1, 2, 3, 4, or 5 substituents    selected from the group consisting of F, Cl, Br, and I;-   L¹ means a ligand, preferably P(R²)₃ wherein R² means unsubstituted    or substituted, straight chain or branched C₁-C₁₄ alkyl,    unsubstituted or substituted C₆-C₂₄ aryl, or unsubstituted or    substituted C₃-C₂₀ cycloalkyl or an N-heterocyclic carbene ligand;

Such transition metal complexes according to general formula (VI) areimportant intermediates in order to produce the inventive transitionmetal complexes according to general formulae (I) and (IV).

The invention further relates to a novel process for preparing thetransition metal complexes according to general formula (II) comprisingreacting a compound of general formula (VII)

wherein

-   X means O or S;-   D means S, O, PR², or NR² with R² meaning straight chain or branched    C₁-C₁₄ alkyl, preferably straight chain or branched C₁-C₆ alkyl,    C₃-C₈ cycloalkyl, preferably C₅-C₆ cycloalkyl, C₆-C₂₄ aryl,    preferably phenyl;-   Y means a divalent moiety, preferably unsubstituted or substituted    C₂-C₆ alkylene, preferably 1,2-ethylene, 1,3-propylene, or    1,4-butylene, or a unsubstituted or substituted C₆-C₁₀ arylene    group, preferably 1,2-phenylene or 2,3-napthylene;-   R means unsubstituted or substituted C₆-C₁₄, preferably C₆-C₁₀ aryl,    more preferably phenyl with none, 1, 2, 3, 4, or 5 substituents    selected from the group consisting of F, Cl, Br, and I;

either with a M-based complex containing at least one L¹ ligand,preferably with a complex of general formula (VIII)M(L¹)₃(H)₂  (VIII)

-   -   wherein    -   M is Ru, Os or Fe; and    -   L¹ means a ligand, preferably P(R²)₃ wherein R² means        substituted or unsubstituted, straight chain or branched C₁-C₁₄        alkyl, substituted or unsubstituted C₆-C₂₄ aryl, or substituted        or unsubstituted C₃-C₂₀ cycloalkyl or an N-heterocyclic carbene        ligand;

or with a M⁰ complex, preferably with a M⁰ complex of general formula(IX)M(L³)_(t)  (IX)

-   -   wherein    -   t is 2, 3, 4, 5, or 6 and    -   L³ are identical or different and represent coordinated,        straight chain or cyclic olefins and arenes, preferably        cyclooctadiene and cyclooctatriene

and with a ligand L¹ having the same meanings as given for generalformula (VIII).

The invention further relates to a novel process for preparingtransition metal complexes according to general formula (II) comprisingreacting a compound of general formula (X)

wherein

-   M, R, L¹ shall have the same meanings as outlined for general    formula (II) and-   X² are identical or different and represent an anionic ligand,    preferably halide, more preferably F, Cl, Br or I, most preferably    Cl;

with a compound of general formula (XI)D[(Y—X)⁻K⁺]₂  (XI)wherein

-   D, X, Y shall have the same meanings as outlined for general    formula (II) and-   K⁺ shall mean any mono charged cation or any equivalent therof,    preferably an alkali metal cation, more preferably Li⁻, Na⁺ or K⁺,    or an earth alkali metal cation, more preferably ½Ca²⁺ or ½Mg²⁺

Furtheron the present invention relates to the use of the complexesaccording to general formula (I) as catalysts, preferably for convertingC═C double bond containing substrates in metathesis reactions, morepreferably ring-closing metatheses (RCM), cross-metatheses (CM) or aring-opening metatheses (ROMP), or for hydrogenating C═C double bondcontaining substrates.

Furtheron the present invention relates to the use of the complexesaccording to general formula (IV) as catalysts, preferably forconverting C═C double bond containing substrates in metathesisreactions, more preferably ring-closing metatheses (RCM),cross-metatheses (CM) or a ring-opening metatheses (ROMP), or forhydrogenating C═C double bond containing substrates.

In particular the present invention relates to a process for preparingcompounds by subjecting a starting compound to a metathesis reaction ora hydrogenation reaction in the presence of a complex according togeneral formula (I) or (IV).

In particular the present invention relates to a process for preparing anitrile rubber with a weight average molecular weight M_(w)′ bysubjecting a starting nitrile rubber having a weight average molecularweight M_(w) to a cross-metathesis reaction in the presence complexaccording to general formula (I), wherein the weight average molecularweight of the starting nitrile rubber M_(w) is higher than the weightaverage molecular weight M_(w) of the nitrile rubber prepared.

In particular the present invention relates to a process for preparing anitrile rubber with a weight average molecular weight M_(w)′ bysubjecting a starting nitrile rubber having a weight average molecularweight M_(w) to a cross-metathesis reaction in the presence complexaccording to general formula (IV), wherein the weight average molecularweight of the starting nitrile rubber M_(w) is higher than the weightaverage molecular weight M_(w) of the nitrile rubber prepared.

In a further particular embodiment the present invention relates to aprocess for preparing partially or fully hydrogenated nitrile rubbers byhydrogenating a starting nitrile rubber in the presence of a complexhaving general formula (I).

In a further particular embodiment the present invention relates to aprocess for preparing partially or fully hydrogenated nitrile rubbers byhydrogenating a starting nitrile rubber in the presence of a complexhaving general formula (IV).

DRAWINGS

FIG. 1 contains the graph relating to Table 1 showing the conversion ofthe Ring Closing Metathesis of Diethyldiallylmalonate depending on thereaction time.

FIG. 2 contains the graph relating to Table 2 showing the conversion ofRing Opening Polymerization of 1,5-cyclooctadiene depending on thereaction time.

FIG. 3 contains the graph relating to Table 3 showing the conversion ofthe Cross Metathesis of 5-hexenyl acetate and methyl methacrylatedepending on the reaction time.

FIG. 4 contains the graph relating to Table 4 showing the conversion ofthe Ring Closing Metathesis of Diethyldiallylmalonate depending on thereaction time.

FIG. 5 contains the graph relating to Table 5 showing the conversion ofthe Ring Opening Polymerization of 1,5-cyclooctadiene depending on thereaction time.

FIG. 6 contains the graph relating to Table 6 showing the conversion ofthe Cross Metathesis of 5-hexenyl acetate and methyl methacrylatedepending on the reaction time.

FIG. 7 contains the graph relating to Table 7 showing the conversion ofthe Ring Closing Metathesis of diethyl diallyl malonate depending on thereaction time.

DETAILED DESCRIPTION OF THE INVENTION

The novel complexes according to general formula (I) are thermallyrobust and represent excellent catalysts which are suited for catalyzingon the one hand metathesis reactions of a broad variety of unsaturatedsubstrates and on the other hand also hydrogenation reactions of a broadvariety of unsaturated substrates of either low molecular weight orhigher and high molecular weight like oligomers and polymers. Mostimportantly these novel complex catalysts according to general formula(I) are accessible via a cheap and safe route showing high yields.Favourably the preferred synthesis route does not necessarily involvethe use of Grubbs-type structures, like Grubbs I catalyst.

The same applies to the novel complexes according to general formula(IV). Besides from being important intermediates for preparing thecomplexes according to general formula (I) as shown above they alsorepresent thermally robust, active catalysts which are suited forcatalyzing hydrogenation reactions of a broad variety of unsaturatedsubstrates of either low molecular weight or higher and high molecularweight like oligomers and polymers. Like the complexes of generalformula (I) they can be prepared with high conversions via differentroutes, preferably via converting compounds of general formula (VII)thereby avoiding the use of Grubbs-type structures, like Grubbs Icatalyst.

The term “substituted” used for the purposes of the present patentapplication means that a hydrogen atom on an indicated radical or atomhas been replaced by one of the groups indicated in each case, with theproviso that the valency of the atom indicated is not exceeded and thesubstitution leads to a stable compound.

For the purposes of the present patent application and invention, allthe definitions of radicals, parameters or explanations given above orbelow in general terms or in preferred ranges can be combined with oneanother in any way, i.e. including combinations of the respective rangesand preferred ranges.

Surprisingly novel transition metal complexes having general formula (I)could be provided

wherein

-   M means Ru, Os or Fe;-   X means O or S;-   D means S, O, PR², or NR² with R² meaning straight chain or branched    C₁-C₁₄ alkyl, preferably straight chain or branched C₁-C₆ alkyl,    C₃-C₈ cycloalkyl, preferably C₃-C₆ cycloalkyl, C₆-C₂₄ aryl,    preferably phenyl;-   Y means a divalent moiety, preferably unsubstituted or substituted    C₂-C₆ alkylene, preferably 1,2-ethylene, 1,3-propylene, or    1,4-butylene, or a unsubstituted or substituted C₆-C₁₀ arylene    group, preferably 1,2-phenylene or 2,3-napthylene;-   R means unsubstituted or substituted C₆-C₁₄, preferably C₆-C₁₀ aryl,    more preferably phenyl with none, 1, 2, 3, 4, or 5 substituents    selected from the group consisting of F, Cl, Br, and I;-   L¹ means a ligand, preferably P(R²)₃ wherein R² means unsubstituted    or substituted, straight chain or branched C₁-C₁₄ alkyl,    unsubstituted or substituted C₆-C₂₄ aryl, or unsubstituted or    substituted C₃-C₂₀ cycloalkyl or an N-heterocyclic carbene ligand;-   Z means B, Al, Ga, or In, preferably B;-   R¹ are identical or different and represent F, Cl, Br, I, preferably    Cl, unsubstituted or substituted, straight chain or branched C₁-C₁₄    alkyl, preferably C₁-C₆ alkyl, C₃-C₈ cycloalkyl, preferably C₅-C₆    cycloalkyl, unsubstituted or substituted C₆-C₂₄ aryl, preferably    phenyl;-   X¹ means F, Cl, Br, or I.-   L² is a two electron donor ligand, preferably CH₃CN, pyridine or    tetrahydrofurane;-   n is either 0 or 1;-   Q is either P, B, Al, As, Ga or Sb, preferably P or B,-   R³ are identical or different and represent F, Cl, Br, I, preferably    F, unsubstituted or substituted, straight chain or branched C₁-C₁₄    alkyl, preferably C₁-C₆ alkyl, C₃-C₈ cycloalkyl, preferably C₅-C₆    cycloalkyl, unsubstituted or substituted C₆-C₂₄ aryl, preferably    phenyl or (C₆F₅), and-   m is 4, 5 or 6, preferably 4 or 6.

The general, preferred, more preferred, even more preferred and mostpreferred embodiments for the meanings of M, X, D, Y, R, L¹ in generalformula (I), as provided above and in the following, shall apply notonly to general formula (I) but also to all other general formulae (II)et seq. given in the present application to the extent the respectivegroup or moiety occurs in such general formula. For the sake of aconcise specification the manyfold repetition of such preferred, morepreferred, even more preferred and most preferred embodiments for themeanings of M, X, D, Y, R, and L¹ in each general formula shall beavoided.

M represents Ru, Os or Fe, preferably Ru.

X means O or S.

D means S, O, PR², or NR² with R² meaning straight chain or branchedC₁-C₁₄ alkyl, preferably straight chain or branched C₁-C₆ alkyl, C₃-C₈cycloalkyl, preferably C₅-C₆ cycloalkyl, C₆-C₂₄ aryl, preferably phenyl.

Y means a divalent moiety, preferably unsubstituted or substituted C₂-C₆alkylene, more preferably 1,2-ethylene, 1,3-propylene, or 1,4-butylene,most preferably 1,2-ethylene, or a unsubstituted or substituted C₆-C₁₀arylene group, preferably 1,2-phenylene or 2,3-napthylene. Y can besubstituted by one or more substituents, preferably selected from thegroup consisting of SiZ₂CH₂ or SiZ₂CH₂CH₂ with Z being C₁-C₆ alkyl orC₁-C₆ alkoxy.

R means unsubstituted or substituted C₆-C₁₄, preferably C₆-C₁₀ aryl,more preferably phenyl with none, 1, 2, 3, 4, or 5 substituents selectedfrom the group consisting of F, Cl, Br, and I;

Z means B, Al, Ga, or In, preferably B.

R¹ are identical or different and represent F, Cl, Br, I, preferably Cl,unsubstituted or substituted, straight chain or branched C₁-C₁₄ alkyl,preferably C₁-C₆ alkyl, C₃-C₈ cycloalkyl, preferably C₅-C₆ cycloalkyl,unsubstituted or substituted C₆-C₂₄ aryl, preferably phenyl;

X¹ means F, Cl, Br, or I.

L² is a two electron donor ligand, preferably CH₃CN, pyridine ortetrahydrofurane; and n is either 0 or 1;

Q is either P, B, Al, As, Ga or Sb, preferably P or B,

R³ are identical or different and represent F, Cl, Br, I, preferably F,unsubstituted or substituted, straight chain or branched C₁-C₁₄ alkyl,preferably C₁-C₆ alkyl, C₃-C₈ cycloalkyl, preferably C₅-C₆ cycloalkyl,unsubstituted or substituted C₆-C₂₄ aryl, preferably phenyl or (C₆F₅),and

m is 4, 5 or 6, preferably 4 or 6.

L¹ means a ligand, preferably either P(R²)₃ wherein R² are identical ordifferent and represent straight chain or branched C₁-C₁₄ alkyl,preferably C₁-C₈ alkyl, C₆-C₂₄ aryl, C₃-C₂₀ cycloalkyl, each of whichmay be substituted or unsubstituted, or an N-heterocyclic carbeneligand.

If L¹ represents a ligand P(R²)₃, R² are identical or different andpreferably mean straight chain or branched C₁-C₈ alkyl, more preferablymethyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, tert-butyl, orneopentyl, C₆-C₁₄ aryl, more preferably phenyl or naphthyl, or C₃-C₁₀cycloalkyl, more preferably cyclopentyl or cyclohexyl wherein each ofthe aforementioned groups may be substituted by one or moresubstitutents more preferably selected from the group consisting ofhalogen, even more preferably F, Cl, Br or I, SO₃Na, C₁-C₈-alkyl,optionally substituted by one or more F, Cl, Br or I, C₆-C₁₄ aryl, morepreferably phenyl or naphthyl, and C₁-C₅-alkoxy.

Most preferably P(R²)₃ represents PPh₃, P(p-Tol)₃, P(o-Tol)₃, PPh(CH₃)₂,P(CF₃)₃, P(p-FC₆H₄)₃, P(p-CF₃C₆H₄)₃, P(C₆H₄—SO₃Na)₃, P(CH₂C₆H₄—SO₃Na)₃,P(isopropyl)₃, P(CHCH₃(CH₂CH₃))₃, P(cyclopentyl)₃, P(cyclohexyl)₃,P(neopentyl)₃ or P(neophyl)₃.

If L¹ represents a N-heterocyclic carbene ligand this is typically animidazoline or imidazolidine ligand having a structure corresponding tothe general formulae (IM-a), or (IM-b),

wherein

-   R⁴, R⁵, R⁶, R⁷ are identical or different and are each hydrogen,    straight-chain or branched C₁-C₃₀-alkyl, C₃-C₂₀-cycloalkyl,    C₂-C₂₀-alkenyl, C₂-C₂₀-alkynyl, C₆-C₂₄-aryl, C₁-C₂₀-carboxylate,    C₁-C₂₀-alkoxy, C₂-C₂₀-alkenyloxy, C₂-C₂₀-alkynyloxy, C₆-C₂₀-aryloxy,    C₂-C₂₀-alkoxycarbonyl, C₁-C₂₀-alkylthio, C₆-C₂₀-arylthio,    C₁-C₂₀-alkylsulphonyl, C₁-C₂₀-alkylsulphonate, C₆-C₂₀-arylsulphonate    or C₁-C₂₀-alkylsulphinyl-   or in the alternative-   R⁶ and R⁷ have the above mentioned meanings and at the same time R⁴    and R⁵ jointly form a C₆-C₁₀ cyclic structure together with the two    adjacent carbon atoms in the imidazoline or imidazolidine ring.

One or more of the substituents R⁴, R⁵, R⁶, R⁷ can, if appropriate,independently of one another, be substituted by one or moresubstituents, preferably straight-chain or branched C₁-C₁₀-alkyl,C₃-C₈-cycloalkyl, C₁-C₁₀-alkoxy or C₆-C₂₄-aryl, where theseabovementioned substituents may in turn be substituted by one or morefunctional groups, preferably functional groups selected from the groupconsisting of halogen, in particular chlorine or bromine, C₁-C₅-alkyl,C₁-C₅-alkoxy and phenyl.

Merely for the sake of clarity, it may be added that the structures ofthe imidazoline or imidazolidine ligands depicted in the generalformulae (IM-a) and (IM-b) in the present application are equivalent tothe structures (IM-a′), and (IM-b′) which are frequently also found inthe literature for this type of ligands and emphasize the carbenecharacter of the imidazoline or imidazolidine ligand. This appliesanalogously to the associated preferred structures (VIII-a)-(VIII-o)depicted below.

In a preferred embodiment of the catalysts of the general formula (I),R⁴ and R⁵ are each, independently of one another, hydrogen, C₆-C₂₄-aryl,particularly preferably phenyl, straight-chain or branched C₁-C₁₀-alkyl,particularly preferably propyl or butyl, or together with the carbonatoms to which they are bound form a C₆-C₁₀ cycloalkyl or C₆-C₁₀ arylsubstituent, preferably a phenyl ring in structure (IM-a) (structure(IM-a′) respectively) where all the above mentioned substituents may inturn be substituted by one or more further substituents selected fromthe group consisting of straight-chain or branched C₁-C₁₀-alkyl,C₁-C₁₀-alkoxy, C₆-C₂₄-aryl and a functional group selected from thegroup consisting of hydroxy, thiol, thioether, ketone, aldehyde, ester,ether, amine, imine, amide, nitro, carboxylic acid, disulphide,carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate and halogen.

In preferred embodiment of the catalysts of the general formula (I), thesubstituents R⁶ and R⁷ are identical or different and are eachstraight-chain or branched C₁-C₁₀-alkyl, particularly preferred i-propylor neopentyl, C₃-C₁₀-cycloalkyl, particularly preferred adamantyl,C₆-C₂₄-aryl, particularly preferred phenyl, C₁-C₁₀-alkylsulphonate,particularly preferred methanesulphonate, C₆-C₁₀-arylsulphonate,particularly preferred p-toluenesulphonate.

The abovementioned substituents as meanings of R⁶ and R⁷ may besubstituted by one or more further substituents selected from the groupconsisting of straight-chain or branched C₁-C₅-alkyl, in particularmethyl, C₁-C₅-alkoxy, optionally substituted aryl and a functional groupselected from the group consisting of hydroxy, thiol, thioether, ketone,aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid,disulphide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamateand halogen.

In particular, the substituents R⁶ and R⁷ can be identical or differentand are each i-propyl, neopentyl, adamantyl, mesityl or2,6-diisopropylphenyl.

Particularly preferred imidazoline or imidazolidine ligands have thefollowing structures (VIII-a) to (VIII-o), where Ph is in each case aphenyl substituent, Bu is a butyl substituent, Mes is in each case a2,4,6-trimethylphenyl substituent and (iPr)₂Ph is in all cases2,6-diisopropylphenyl.

Preferred Definitions of General Formula (I):

In a preferred embodiment complexes of general formula (I) are providedin which

-   M means Ru-   X means O or S;-   D means S, O, PR², or NR² with R² meaning straight chain or branched    C₁-C₆ alkyl, preferably C₅-C₆ cycloalkyl, C₆-C₁₄ aryl, preferably    phenyl.-   Y means a divalent moiety, preferably unsubstituted or substituted    C₂-C₆ alkylene, more preferably 1,2-ethylene, 1,3-propylene, or    1,4-butylene, most preferably 1,2-ethylene, or a unsubstituted or    substituted C₆-C₁₀ arylene group, preferably 1,2-phenylene or    2,3-napthylene;-   R means unsubstituted or substituted C₆-C₁₄, preferably C₆-C₁₀ aryl,    more preferably phenyl with none, 1, 2, 3, 4, or 5 substituents    selected from the group consisting of F, Cl, Br, and I;-   L¹ means either    -   P(R²)₃ wherein    -   R² are identical or different and preferably mean straight chain        or branched C₁-C₈ alkyl, more preferably methyl, ethyl,        n-propyl, isopropyl, n-butyl, i-butyl, tert-butyl, or neopentyl,        C₆-C₁₄ aryl, more preferably phenyl or naphthyl, or C₃-C₁₀        cycloalkyl, more preferably cyclopentyl or cyclohexyl wherein        each of the aforementioned groups may be substituted by one or        more substitutents more preferably selected from the group        consisting of halogen, even more preferably F, Cl, Br or I,        SO₃Na, C₁-C₈-alkyl, the latter either unsubstituted or        substituted by one or more F, Cl, Br or I, C₆-C₁₄ aryl, more        preferably phenyl or naphthyl, and C₁-C₃-alkoxy.    -   an N-heterocyclic carbene ligand of general formulae (IM-a) or        (IM-b)

-   -   wherein    -   R⁴, R⁵, R⁶, R⁷ are identical or different and are each hydrogen,        straight-chain or branched C₁-C₃₀-alkyl, C₃-C₂₀-cycloalkyl,        C₂-C₂₀-alkenyl, C₂-C₂₀-alkynyl, C₆-C₂₄-aryl, C₁-C₂₀-carboxylate,        C₁-C₂₀-alkoxy, C₂-C₂₀-alkenyloxy, C₂-C₂₀-alkynyloxy,        C₆-C₂₀-aryloxy, C₂-C₂₀-alkoxycarbonyl, C₁-C₂₀-alkylthio,        C₆-C₂₀-arylthio, C₁-C₂₀-alkylsulphonyl, C₁-C₂₀-alkylsulphonate,        C₆-C₂₀-arylsulphonate or C₁-C₂₀-alkylsulphinyl;    -   or in the alternative    -   R⁶ and R⁷ have the above mentioned meanings and at the same time        R⁴ and R⁵ jointly form a C₆-C₁₀ cyclic structure together with        the two adjacent carbon atoms in the imidazoline or        imidazolidine ring;

-   Z means B, Al, Ga, or In, preferably B;

-   R¹ are identical or different and represent F, Cl, Br, I, preferably    Cl, unsubstituted or substituted, straight chain or branched C₁-C₁₄    alkyl, preferably C₁-C₆ alkyl, C₃-C₈ cycloalkyl, preferably C₅-C₆    cycloalkyl, unsubstituted or substituted C₆-C₂₄ aryl, preferably    phenyl;

-   X¹ means F, Cl, Br, or I.

-   L² is a two electron donor ligand, preferably CH₃CN, pyridine or    tetrahydrofurane;

-   n is either 0 or 1,

-   Q is either P, B, Al, As, Ga or Sb, preferably P or B,

-   R³ are identical or different and represent F, Cl, Br, I, preferably    F, unsubstituted or substituted, straight chain or branched C₁-C₁₄    alkyl, preferably C₁-C₆ alkyl, C₃-C₈ cycloalkyl, preferably C₅-C₆    cycloalkyl, unsubstituted or substituted C₆-C₂₄ aryl, preferably    phenyl or (C₆F₅), and

-   m is 4, 5 or 6, preferably 4 or 6.

In an even more preferred embodiment complexes of general formula (I)are provided in which

-   M means Ru-   X means O or S;-   D means S, O, PR², or NR² with R² meaning straight chain or branched    C₁-C₆ alkyl, most preferably C₅-C₆ cycloalkyl, C₆-C₁₄ aryl, most    preferably phenyl.-   Y means 1,2-ethylene or 1,2-phenyl;-   R means phenyl with none, 1, 2, 3, 4, or 5 substituents selected    from the group consisting of F, Cl, Br, and I-   L¹ is selected from the group consisting of PPh₃, P(p-Tol)₃,    P(o-Tol)₃, PPh(CH₃)₂, P(CF₃)₃, P(p-FC₆H₄)₃, P(p-CF₃C₆H₄)₃,    P(C₆H₄—SO₃Na)₃, P(CH₂C₆H₄—SO₃Na)₃, P(isopropyl)₃, P(CHCH₃(CH₂CH₃))₃,    P(cyclopentyl)₃, P(cyclohexyl)₃, P(neopentyl)₃, P(neophyl)₃, and an    N-heterocyclic carbene ligand of general formulae (IM-a) or (IM-b),    wherein R⁶ and R⁷ are identical or different and represent i-propyl,    neopentyl, adamantyl, mesityl or 2,6-diisopropylphenyl, and R⁴ and    R⁵ are identical or different and represent hydrogen, C₆-C₂₄-aryl,    particularly preferably phenyl, straight-chain or branched    C₁-C₁₀-alkyl, particularly preferably propyl or butyl, or together    with the carbon atoms to which they are bound form a C₆-C₁₀    cycloalkyl or C₆-C₁₀ aryl substituent, preferably a phenyl ring;-   Z means B, Al, Ga, or In;-   R¹ are identical or different and represent F, Cl, Br, I, and are    most preferably identical and Cl;-   X¹ means F, Cl, Br, or I, most preferably Cl;-   L² represents CH₃CN, pyridine or tetrahydrofurane;-   n is either 0 or 1,-   Q is either P, B, Al, As, Ga or Sb, preferably P or B,-   R³ are identical or different and represent F, Cl, Br, I, preferably    F, unsubstituted or substituted, straight chain or branched C₁-C₁₄    alkyl, preferably C₁-C₆ alkyl, C₃-C₈ cycloalkyl, preferably C₅-C₆    cycloalkyl, unsubstituted or substituted C₆-C₂₄ aryl, preferably    phenyl or (C₆F₅), and-   m is 4, 5 or 6, preferably 4 or 6.

In a most preferred embodiment complexes of general formula (I) areprovided in which

-   M means Ru-   X means O or S;-   D means S, O, PR², or NR² with R² meaning straight chain or branched    C₁-C₆ alkyl, most preferably C₅-C₆ cycloalkyl, C₆-C₁₄ aryl, most    preferably phenyl.-   Y means 1,2-ethylene or 1,2-phenyl;-   R means phenyl with none or 5 substituents selected from the group    consisting of F, Cl, Br, and I;-   L¹ is selected from the group consisting of PPh₃, P(p-Tol)₃,    P(o-Tol)₃, PPh(CH₃)₂, P(CF₃)₃, P(p-FC₆H₄)₃, P(p-CF₃C₆H₄)₃,    P(C₆H₄—SO₃Na)₃, P(CH₂C₆H₄—SO₃Na)₃, P(isopropyl)₃, P(CHCH₃(CH₂CH₃))₃,    P(cyclopentyl)₃, P(cyclohexyl)₃, P(neopentyl)₃, P(neophyl)₃, and an    N-heterocyclic carbene ligand of the structures (VIII-a) to    (VIII-o);-   Z means B;-   R¹ are identical and represent Cl;-   X¹ means Cl;-   L² represents CH₃CN, pyridine or tetrahydrofurane;-   n is either 0 or 1,-   Q is either P, B, Al, As, Ga or Sb, preferably P or B,-   R³ are identical or different and represent F, Cl, Br, I, preferably    F, unsubstituted or substituted, straight chain or branched C₁-C₁₄    alkyl, preferably C₁-C₆ alkyl, C₃-C₈ cycloalkyl, preferably C₅-C₆    cycloalkyl, unsubstituted or substituted C₆-C₂₄ aryl, preferably    phenyl or (C₆F₅), and-   m is 4, 5 or 6, preferably 4 or 6.

The invention further relates to a process for preparing the complexesaccording to general formula (I) comprising

-   (1) reacting the complex of general formula (II)

-   -   wherein    -   M means Ru, Os or Fe;    -   X means O or S;    -   D means S, O, PR², or NR² with R² meaning straight chain or        branched C₁-C₁₄ alkyl, preferably straight chain or branched        C₁-C₆ alkyl, C₃-C₈ cycloalkyl, preferably C₅-C₆ cycloalkyl,        C₆-C₂₄ aryl, preferably phenyl;    -   Y means a divalent moiety, preferably unsubstituted or        substituted C₂-C₆ alkylene, preferably 1,2-ethylene,        1,3-propylene, or 1,4-butylene, or a unsubstituted or        substituted C₆-C₁₀ arylene group, preferably 1,2-phenylene or        2,3-napthylene;    -   R means unsubstituted or substituted C₆-C₁₄, preferably C₆-C₁₀        aryl, more preferably phenyl with none, 1, 2, 3, 4, or 5        substituents selected from the group consisting of F, Cl, Br,        and I;    -   L¹ means a ligand, preferably P(R²)₃ wherein R² means        unsubstituted or substituted, straight chain or branched C₁-C₁₄        alkyl, unsubstituted or substituted C₆-C₂₄ aryl, or        unsubstituted or substituted C₃-C₂₀ cycloalkyl or an        N-heterocyclic carbene ligand;    -   with a compound of general formula (III)        ZX¹(R¹)₂  (III)    -   wherein    -   Z means B, Al, Ga or In, preferably B;    -   X¹ means F, Cl, Br, or I; preferably Cl; and    -   R¹ are identical or different and represent F, Cl, Br, I,        preferably Cl, unsubstituted or substituted, straight chain or        branched C₁-C₁₄—, preferably C₁-C₆ alkyl, C₃-C₈ cycloalkyl,        preferably C₃-C₆ cycloalkyl, unsubstituted or substituted C₆-C₂₄        aryl, preferably phenyl;    -   resulting in a complex according to general formula (IV)

-   -   wherein M, X, D, Y, R, X¹, and R¹ have the same meanings as        outlined above for general formulae (II) and (III), and    -   reacting the compound of general formula (IV) with a compound of        general formula (Va)        Z(R¹)₃  (Va)    -   wherein    -   Z means B, Al, Ga or In; preferably B, and    -   R¹ are identical or different and represent F, Cl, Br, I,        preferably Cl, unsubstituted or substituted, straight chain or        branched C₁-C₁₄—, preferably C₁-C₆ alkyl, C₃-C₈ cycloalkyl,        preferably C₃-C₆ cycloalkyl, unsubstituted or substituted C₆-C₂₄        aryl, preferably phenyl;    -   or    -   reacting the compound of general formula (IV) with a compound of        general formula (Vb)        GQ(R³)_(m)  (Vb)    -   wherein

-   G is K, Na, Li, Cs, Ag or Cu, preferably K,

-   Q is either P, B, Al, As, Ga or Sb, preferably P or B,

-   R³ are identical or different and represent F, Cl, Br, I, preferably    F, unsubstituted or substituted, straight chain or branched C₁-C₁₄    alkyl, preferably C₁-C₆ alkyl, C₃-C₈ cycloalkyl, preferably C₅-C₆    cycloalkyl, unsubstituted or substituted C₆-C₂₄ aryl, preferably    phenyl or (C₆F₅), and

-   m is 4, 5 or 6, preferably 4 or 6.    -   to obtain the complex catalyst according to general formula (I)        with n being 0 and

-   (2) optionally adding the ligand L² to obtain the complex catalyst    according to general formula (I) with n being 1, wherein such ligand    L² may be added simultaneously to the compound of general formula    (Va) or (Vb) in step 2 or thereafter.

The above described synthesis of the complexes of general formula (I) issummarized in the following scheme:

wherein M, X, D, Y, R, L¹, Z, R¹, L², Q, R³, m and n have the samegeneral, preferred, more preferred and most preferred meanings asoutlined above.

In the first step of such activation reaction the Lewis acid ZX¹(R¹)₂containing a halogen transfers the halide to the metal and bridgesbetween the two X ligands. Secondly, the halogen which was transferredto the metal is abstracted by the second Lewis acid, Z(R¹)₃ to generatea cationic metal-alkylidene complex which is active for olefinmetathesis.

Reaction Conditions for Synthesis of Complexes of General Formula (I):

Such synthesis of the complexes of general formula (I) starting fromcomplexes of general formula (II) is typically carried out in an organicsolvent, preferably, dichloromethane and at temperatures in the range of5 to 50° C., preferably of from 10 to 40° C. Step 1 and step 2 aretypically carried out in the same solvent. The compounds of general(III) and (Va) may be identical or different, preferably they areidentical. In step (1) the complex of general formula (II) and the Lewisacid (III), ZX¹(R¹)₂, are preferably used in an equimolar ratio. In step(2) the complex of general formula (IV) and the Lewis acid (Va), Z(R¹)₃,or (Vb) GQ(R³)_(m) are used in a molar ratio of 1:(1-2), preferably 1:1.In case the Lewis acid (III), Z(R¹)₃, is the same as Lewis acid (Va),ZX¹(R¹)₂, this reaction can also be performed in one step only, with themolar ratio of the complex of general formula (II) to the ZX¹(R¹)₂ is 1:(2-3), preferably 1: (2). The complexes of formula (I) obtained aftersuch process can be used in situ as catalysts, i.e. without isolatingthem. In the alternative a ligand L² can be added and the resultingcomplex with n being 1 can then be isolated.

Typical embodiments of the process for preparing complexes of generalformula (I) are:

Embodiment 1

Embodiment 2

Embodiment 3

Embodiment 4

Embodiment 5

Embodiment 6

Embodiment 7

Embodiment 8

Embodiment 9

Embodiment 10

The invention further relates to novel transition metal complexesaccording to general formula (VI)

wherein

-   M means Ru, Os or Fe;-   X means O or S;-   D means S, O, or PR² with R² meaning straight chain or branched    C₁-C₁₄ alkyl, preferably straight chain or branched C₁-C₆ alkyl,    C₃-C₈ cycloalkyl, preferably C₃-C₆ cycloalkyl, C₆-C₂₄ aryl,    preferably phenyl;-   Y means a divalent moiety, preferably unsubstituted or substituted    C₂-C₆ alkylene, preferably 1,2-ethylene, 1,3-propylene, or    1,4-butylene, or a unsubstituted or substituted C₆-C₁₀ arylene    group, preferably 1,2-phenylene or 2,3-napthylene;-   R means unsubstituted or substituted C₆-C₁₄, preferably C₆-C₁₀ aryl,    more preferably phenyl with none, 1, 2, 3, 4, or 5 substituents    selected from the group consisting of F, Cl, Br, and I;-   L¹ means a ligand, preferably P(R²)₃ wherein R² means unsubstituted    or substituted, straight chain or branched C₁-C₁₄ alkyl,    unsubstituted or substituted C₆-C₂₄ aryl, or unsubstituted or    substituted C₃-C₂₀ cycloalkyl or an N-heterocyclic carbene ligand;

The invention further relates to two different processes for preparingthe transition metal complexes according to general formula (II) whichare hereinafter also referred to as Route A and Route B.

Route A:

Route A represents a novel process for preparing the transition metalcomplexes according to general formula (II) comprising reacting acompound of general formula (VII)

wherein

-   X means O or S;-   D means S, O, PR², or NR² with R² meaning straight chain or branched    C₁-C₁₄ alkyl, preferably straight chain or branched C₁-C₆ alkyl,    C₃-C₈ cycloalkyl, preferably C₅-C₆ cycloalkyl, C₆-C₂₄ aryl,    preferably phenyl;-   Y means a divalent moiety, preferably unsubstituted or substituted    C₂-C₆ alkylene, preferably 1,2-ethylene, 1,3-propylene, or    1,4-butylene, or a unsubstituted or substituted C₆-C₁₀ arylene    group, preferably 1,2-phenylene or 2,3-napthylene;-   R means unsubstituted or substituted C₆-C₁₄, preferably C₆-C₁₀ aryl,    more preferably phenyl with none, 1, 2, 3, 4, or 5 substituents    selected from the group consisting of F, Cl, Br, and I;

either with a M-based complex containing at least one L¹ ligand,preferably a complex of general formula (VIII)M(L¹)₃(H)₂  (VIII)

-   -   wherein    -   M is Ru, Os or Fe; and    -   L¹ means a ligand, preferably P(R²)₃ wherein R² means        substituted or unsubstituted, straight chain or branched C₁-C₁₄        alkyl, substituted or unsubstituted C₆-C₂₄ aryl, or substituted        or unsubstituted C₃-C₂₀ cycloalkyl or an N-heterocyclic carbene        ligand;

or with a M⁰ complex, preferably a M⁰ complex of general formula (IX)M(L³)_(t)  (IX)

-   -   wherein    -   t is 2, 3, 4, 5, or 6 and    -   L³ are identical or different and represent coordinated,        straight chain or cyclic olefins and arenes, preferably        cyclooctadiene and cyclooctatriene

and a ligand L¹ having the same meanings as given for general formula(VIII).

Optionally a further ligand L¹ being different from L¹ in the M-basedcomplex, preferably the complex of formula (VIII), can be added andthereby introduced into the compound of general formula (II).

Route A for preparing the transition metal complexes according togeneral formula (II) is an unprecedented route which is shown in totalin the following scheme:

wherein D, Y, X, R, L¹ have the meanings outlined above with regard togeneral formula (II).

As M⁰ source of the general formula M(L¹)₃(H)₂ or M(L³)_(t) compoundslike Ru(PPh₃)₃(H)₂, Ru(cod)(cot), and Ru(H₂)₂(H)₂(PCy₃)₂ can be used.

Alternatively, Ru(PPh₃)₃HCl or Ru(PCy₃)₂(H₂)HCl can be used as a M-basedcomplex containing at least one L¹ ligand.

The compounds of general formula (VII) are accessible via methodssufficiently disclosed in the prior art or known to the person skilledin the art as e.g. J. Chem. Soc., Perkin Trans. 1, 1004, 707-715 withregard to thioacetals.

Reaction Conditions for complexes with general formula (II) via Route A:

The synthesis of the complexes of general formula (II) via Route A istypically carried out in an organic solvent, preferably in benzene, andat temperatures in the range of 20 to 80° C. Reaction times maytypically be chosen in the range of from 2 to 24 hours. The reactionsare typically carried out under oxygen and water free conditions. If adifferent L¹ is desired, it can be added any time during the reaction.

Route B:

Route B represents an alternative process for preparing the transitionmetal complexes according to general formula (II) comprising reacting acompound of general formula (IX)

wherein

-   -   M, R, L¹ shall have the same meanings as outlined for general        formula (II) and    -   X² are identical or different and represent an anionic ligand,        preferably halide, more preferably F, Cl, Br or I, most        preferably Cl;

with a compound of general formula (XI)D[(Y—X)⁻K⁺]₂  (XI)

wherein

-   D, X, Y shall have the same meanings as outlined for general    formula (II) and-   K⁺ shall mean any mono charged cation or any equivalent thereof,    preferably an alkali metal cation, more preferably Li⁺, Na⁺ or K⁺,    or an earth alkali metal cation, more preferably ½Ca²⁺ or ½Mg²⁺.

This Route B for preparing novel transition metal complexes according togeneral formula (II) is shown in total in the following scheme:

Furtheron the present invention relates to the use of the complexesaccording to general formula (I) as catalysts, preferably for convertingC═C double bond containing substrates in metathesis reactions, morepreferably ring-closing metatheses (RCM), cross-metatheses (CM) or aring-opening metatheses (ROMP), or for hydrogenating C═C double bondcontaining substrates.

Additionally the invention relates to the use of the complexes accordingto general formula (IV) as catalysts, preferably for converting C═Cdouble bond containing substrates in metathesis reactions, morepreferably ring-closing metatheses (RCM), cross-metatheses (CM) or aring-opening metatheses (ROMP), or for hydrogenating C═C double bondcontaining substrates.

In particular the present invention relates to a process for preparingcompounds by subjecting a starting compound to a metathesis reaction ora hydrogenation reaction in the presence of a complex according togeneral formula (I) or (IV).

In a further particular embodiment the present invention relates to aprocess for preparing partially or fully hydrogenated nitrile rubbers byhydrogenating a starting nitrile rubber in the presence of a complexhaving general formula (I) or general formula (IV).

Hydrogenation:

Substrates to be Hydrogenated:

The process of the present invention is broadly applicable to thehydrogenation of a variety of substrates, including terminal olefins,internal olefins, cyclic olefins, conjugated olefins, and any furtherolefins having at least one carbon-carbon double bond and additionallyat least one further polar unsaturated double or triple bond. Theprocess is also applicable to the hydrogenation of polymers havingcarbon-carbon double bonds. Such polymers may represent homo-, co- orterpolymers.

As a terminal olefin or alkene, it is possible to hydrogenate ahydrocarbon compound with a terminal unsaturated carbon-carbon doublebond having the general formula C_(n)H_(2n). The terminal olefin can bea straight-chain or a branched hydrocarbon compound of any length,preferably 1-hexene.

As an internal olefin or alkene, it is possible to hydrogenate ahydrocarbon compound with an internal unsaturated carbon-carbon doublebond having the general formula C_(n)H_(2n). The internal olefin can bea straight-chain or a branched hydrocarbon of any length, preferably2-hexene.

As a cyclic olefin or cycloalkene, it is possible to hydrogenate ahydrocarbon compound with a cyclic unsaturated carbon-carbon double bondhaving the general formula C_(n)H_(2n-2). The cyclic olefin can be aring of any size, preferably cyclohexene.

As a conjugated olefin or dialkene, it is possible to hydrogenate ahydrocarbon compound with conjugated carbon-carbon unsaturated doublebonds. The conjugation can be a straight-chain or a branched hydrocarbonof any length, preferably styrene.

As an olefin, it is also possible to selectively hydrogenate ahydrocarbon compound with at least one unsaturated carbon-carbon doublebond and least one other unsaturated polar double or triple bond. Suchunsaturated polar bonds are surprisingly left unaltered. Thecarbon-carbon double bond in such olefins can be of any nature includingterminal, internal, cyclic and conjugated ones. The additionalunsaturated polar bond can be of any nature with preference given tocarbon-nitrogen, carbon-phosphorus, carbon-oxygen, and carbon-sulfurunsaturated polar bonds.

Polymers having carbon-carbon double bonds may also be subjected to theinventive process. Such polymers preferably comprise repeating unitsbased on at least one conjugated diene monomer.

The conjugated diene can be of any nature. In one embodiment (C₄-C₆)conjugated dienes are used. Preference is given to 1,3-butadiene,isoprene, 1-methylbutadiene, 2,3-dimethylbutadiene, piperylene,chloroprene, or mixtures thereof. More preference is given to1,3-butadiene, isoprene or mixtures thereof. Particular preference isgiven to 1,3-butadiene.

In a further embodiment polymers having carbon-carbon double bonds maybe subjected to the inventive process which comprise repeating units ofnot only at least one conjugated diene as monomer (a) but additionallyat least one further copolymerizable monomer (b). Examples of suitablemonomers (b) are olefins, such as ethylene or propylene.

Further examples of suitable monomers (b) are vinylaromatic monomers,such as styrene, alpha-methyl styrene, o-chlorostyrene or vinyltoluenes,vinylesters of aliphatic or branched C₁-C₁₈ monocarboxylic acids, suchas vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate,vinyl hexanoate, vinyl 2-ethylhexanoate, vinyl decanoate, vinyl laurateand vinyl stearate.

A preferred polymer to be used in the present invention is a copolymerof 1,3-butadiene and styrene or alpha-methylstyrene. Said copolymers mayhave a random or block type structure.

Further examples of suitable monomers (b) are esters of ethylenicallyunsaturated monocarboxylic acids or mono- or diesters of dicarboxylicacids with generally C₁-C₁₂ alkanols, e.g. esters of acrylic acid,methacrylic acid, maleic acid, fumaric acid and itaconic acid with e.g.methanol, ethanol, n-propanol, isopropanol, 1-butanol, 2-butanol,isobutanol, tert-butanol, n-hexanol, 2-ethylhexanol, orC₅-C₁₀-cycloalkanols, such as cyclopentanol or cyclohexanol, and ofthese preferably the esters of acrylic and/or methacrylic acid, examplesbeing methyl methacrylate, n-butyl methacrylate, tert-butylmethacrylate, n-butyl acrylate, tert-butyl acrylate, and 2-ethylhexylacrylate.

The inventive process may be further used to hydrogenate so-callednitrile rubbers. Nitrile rubbers (“NBR”) represent copolymers orterpolymers containing repeating units of at least one conjugated diene,at least one α,β-unsaturated nitrile monomer and, if appropriate, one ormore further copolymerizable monomers.

The conjugated diene in such nitrile rubbers can be of any nature.Preference is given to using (C₄-C₆)-conjugated dienes. Particularpreference is given to 1,3-butadiene, isoprene, 2,3-dimethylbutadiene,piperylene or mixtures thereof. In particular, use is preferably made of1,3-butadiene or isoprene or mixtures thereof. Very particularpreference is given to 1,3-butadiene.

As α,β-unsaturated nitrile monomer, it is possible to use any knownα,β-unsaturated nitrile, with preference being given to(C₃-C₅)-α,β-unsaturated nitriles such as acrylonitrile,methacrylonitrile, ethacrylonitrile or mixtures thereof. Particularlypreference is given to acrylonitrile.

A particularly preferred nitrile rubber to be subjected to hydrogenationaccording to the invention is thus a copolymer of acrylonitrile and1,3-butadiene.

In addition to the conjugated diene and the α,β-unsaturated nitrile, itis possible to use one or more further copolymerizable monomers known tothose skilled in the art, e.g. termonomers containing carboxyl groups,like α,β-unsaturated monocarboxylic acids, their esters or amides,α,β-unsaturated dicarboxylic acids, their monoesters or diesters, ortheir corresponding anhydrides or amides.

As α,β-unsaturated monocarboxylic acids it is possible to use acrylicacid and methacrylic acid.

It is also possible to employ esters of the α,β-unsaturatedmonocarboxylic acids, preferably their alkyl esters and alkoxyalkylesters. Preference is given to the alkyl esters, especially C₁-C₁₈ alkylesters, of the α,β-unsaturated monocarboxylic acids, Particularpreference is given to alkyl esters, especially C₁-C₁₈ alkyl esters, ofacrylic acid or of methacrylic acid, more particularly methyl acrylate,ethyl acrylate, propyl acrylate, n-butyl acrylate, tert-butyl acrylate,2-ethylhexyl acrylate, n-dodecyl acrylate, methyl methacrylate, ethylmethacrylates, butyl methacrylate and 2-ethylhexyl methacrylate. Alsopreferred are alkoxyalkyl esters of the α,β-unsaturated monocarboxylicacids, more preferably alkoxyalkyl esters of acrylic acid or ofmethacrylic acid, more particular C₂-C₁₂ alkoxyalkyl esters of acrylicacid or of methacrylic acid, very preferably methoxymethyl acrylate,methoxyethyl(meth)acrylate, ethoxyethyl(meth)acrylate andmethoxyethyl(meth)acrylate. Use may also be made of mixtures of alkylesters, such as those mentioned above, for example, with alkoxyalkylesters, in the form of those mentioned above, for example. Use may alsobe made of cyanoalkyl acrylate and cyanoalkyl methacrylates in which theC atom number of the cyanoalkyl group is 2-12, preferably α-cyanoethylacrylate, β-cyanoethyl acrylate and cyanobutyl methacrylate. Use mayalso be made of hydroxyalkyl acrylates and hydroxyalkyl methacrylate inwhich the C atom number of the hydroxyalkyl groups is 1-12, preferably2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and 3-hydroxypropylacrylate; use may also be made of fluorine-substitutedbenzyl-group-containing acrylates or methacrylates, preferablyfluorobenzyl acrylate, and fluorobenzyl methacrylate. Use may also bemade of acrylates and methacrylates containing fluoroalkyl groups,preferably trifluoroethyl acrylate and tetrafluoropropyl methacrylate.Use may also be made of α,β-unsaturated carboxylic esters containingamino groups, such as dimethylaminomethyl acrylate and diethylaminoethylacrylate.

As copolymerizable monomers it is possible, furthermore, to useα,β-unsaturated dicarboxylic acids, preferably maleic acid, fumaricacid, crotonic acid, itaconic acid, citraconic acid and mesaconic acid.Use may be made, furthermore, of α,β-unsaturated dicarboxylicanhydrides, preferably maleic anhydride, itaconic anhydride, citraconicanhydride and mesaconic anhydride.

It is possible, furthermore, to use monoesters or diesters ofα,β-unsaturated dicarboxylic acids.

These α,β-unsaturated dicarboxylic monoesters or diesters may be, forexample, alkyl esters, preferably C₁-C₁₀ alkyl, more particularly ethyl,n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl or n-hexyl esters,alkoxyalkyl esters, preferably C₂-C₁₂ alkoxyalkyl, more preferablyC₃-C₈-alkoxyalkyl, hydroxyalkyl, preferably C₁-C₁₂ hydroxyalkyl, morepreferably C₂-C₈ hydroxyalkyl, cycloalkyl esters, preferably C₅-C₁₂cycloalkyl, more preferably C₆-C₁₂ cycloalkyl, alkylcycloalkyl esters,preferably C₆-C₁₂ alkylcycloalkyl, more preferably C₇-C₁₀alkylcycloalkyl, aryl esters, preferably C₆-C₁₄ aryl esters, theseesters being monoesters or diesters, and it also being possible, in thecase of the diesters, for the esters to be mixed esters.

Particularly preferred alkyl esters of α,β-unsaturated monocarboxylicacids are methyl(meth)acrylate, ethyl(meth)acrylate,propyl(meth)acrylate, n-butyl(meth)acrylate, t-butyl(meth)acrylate,hexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, octyl(meth)acrylate,2-propylheptyl acrylate and lauryl(meth)acrylate. More particularly,n-butyl acrylate is used.

Particularly preferred alkoxyalkyl esters of the α,β-unsaturatedmonocarboxylic acids are methoxyethyl(meth)acrylate,ethoxyethyl(meth)acrylate and methoxyethyl(meth)acrylate. Moreparticularly, methoxyethyl acrylate is used.

Particularly preferred hydroxyalkyl esters of the α,β-unsaturatedmonocarboxylic acids are hydroxyethyl(meth)acrylate,hydroxypropyl(meth)acrylate and hydroxybutyl(meth)acrylate.

Other esters of the α,β-unsaturated monocarboxylic acids that are usedare additionally, for example, polyethylene glycol(meth)acrylate,polypropylene glycol(meth)acrylate, glycidyl(meth)acrylate,epoxy(meth)acrylate, N-(2-hydroxyethyl)acrylamides,N-(2-hydroxymethyl)acrylamides and urethane(meth)acrylate.

Examples of α,β-unsaturated dicarboxylic monoesters encompass

-   maleic acid monoalkyl esters, preferably monomethyl maleate,    monoethyl maleate, monopropyl maleate and mono-n-butyl maleate;-   maleic acid monocycloalkyl esters, preferably monocyclopentyl    maleate, monocyclohexyl maleate and monocycloheptyl maleate;-   maleic acid monoalkyl cycloalkyl esters, preferably monomethyl    cyclopentyl maleate and monoethyl cyclohexyl maleate;-   maleic acid monoaryl esters, preferably monophenyl maleate;-   maleic acid monobenzyl esters, preferably monobenzyl maleate;-   fumaric acid monoalkyl esters, preferably monomethyl fumarate,    monoethyl fumarate, monopropyl fumarate and mono-n-butyl fumarate;-   fumaric acid monocycloalkyl esters, preferably monocyclopentyl    fumarate, monocyclohexyl fumarate and monocycloheptyl fumarate;-   fumaric acid monoalkyl cycloalkyl esters, preferably monomethyl    cyclopentyl fumarate and monoethyl cyclohexyl fumarate;-   fumaric acid monoaryl esters, preferably monophenyl fumarate;-   fumaric acid monobenzyl esters, preferably monobenzyl fumarate;-   citraconic acid monoalkyl esters, preferably monomethyl citraconate,    monoethyl citraconate, monopropyl citraconate and mono-n-butyl    citraconate;-   citraconic acid monocycloalkyl esters, preferably monocyclopentyl    citraconate, monocyclohexyl citraconate and monocycloheptyl    citraconate;-   citraconic acid monoalkyl cycloalkyl esters, preferably monomethyl    cyclopentyl citraconate and monoethyl cyclohexyl citraconate;-   citraconic acid monoaryl esters, preferably monophenyl citraconate;-   citraconic acid monobenzyl esters, preferably monobenzyl    citraconate;-   itaconic acid monoalkyl esters, preferably monomethyl itaconate,    monoethyl itaconate, monopropyl itaconate and mono-n-butyl    itaconate;-   itaconic acid monocycloalkyl esters, preferably monocyclopentyl    itaconate, monocyclohexyl itaconate and monocycloheptyl itaconate;-   itaconic acid monoalkyl cycloalkyl esters, preferably monomethyl    cyclopentyl itaconate and monoethyl cyclohexyl itaconate;-   itaconic acid monoaryl esters, preferably monophenyl itaconate;-   itaconic acid monobenzyl esters, preferably monobenzyl itaconate.-   Mesaconic acid monoalkyl esters, preferably mesaconic acid monoethyl    esters;

As α,β-unsaturated dicarboxylic diesters it is possible to use theanalogous diesters based on the abovementioned monoester groups, and theester groups may also be chemically different groups.

Preferably the substrate to be hydrogenated is a nitrile rubbercomprising repeating units of at least one conjugated diene, at leastone α,β-unsaturated nitrile and, if appropriate, one or more furthercopolymerizable monomers, preferably a nitrile rubber comprisingrepeating units of at least one conjugated diene selected from the groupconsisting of 1,3-butadiene, isoprene, 2,3-dimethylbutadiene, piperyleneand mixtures thereof, at least one α,β-unsaturated nitrile selected fromthe group consisting of acrylonitrile, methacrylonitrile,ethacrylonitrile and mixtures thereof, and optionally of one or morefurther copolymerizable monomers selected from the group consisting ofα,β-unsaturated monocarboxylic, dicarboxylic acids, their esters oramides.

The proportions of conjugated diene and α,β-unsaturated nitrile monomerin the NBR polymers to be used can vary within wide ranges. Theproportion of the conjugated diene or the sum of conjugated dienes isusually in the range from 40 to 90% by weight, preferably in the rangefrom 50 to 85% by weight, based on the total polymer. The proportion ofthe α,β-unsaturated nitrile or the sum of the α,β-unsaturated nitrilesis usually from 10 to 60% by weight, preferably from 15 to 50% byweight, based on the total polymer. The proportions of the monomers ineach case add up to 100% by weight. The additional monomers can bepresent in amounts of from 0 to 40% by weight, preferably from 0.1 to40% by weight, particularly preferably from 1 to 30% by weight, based onthe total polymer. In this case, corresponding proportions of theconjugated diene or dienes and/or the α,β-unsaturated nitrile ornitriles are replaced by the proportions of the additional monomers,with the proportions of all monomers in each case adding up to 100% byweight.

The preparation of such nitrile rubbers by polymerization of theabovementioned monomers is adequately known to those skilled in the artand is comprehensively described in the literature.

Nitrile rubbers which can be used for the purposes of the invention arecommercially available, e.g. as products marketed under the trademarksPerbunan® and Krynac® by Lanxess Deutschland GmbH. The nitrile rubberswhich can be used for the hydrogenation have a Mooney viscosity (ML 1+4at 100° C.) in the range from 30 to 70, preferably from 30 to 50. Thiscorresponds to a weight average molecular weight M_(w) in the range150,000-500,000, preferably in the range 180,000-400,000. The nitrilerubbers used typically have a polydispersity PDI=M_(w)/M_(n) (M_(n) isthe number average molecular weight and M_(n) is the number averagemolecular weight) in the range of 2.0-6.0 and preferably in the range2.0-4.0.

Hydrogenated nitrile rubbers obtained pursuant to this invention canhave a Mooney viscosity (ML 1+4 at 100° C.) in the range of greater than0 up to 150, typically the Mooney viscosity lies in the range of from 5to 150, preferably of from 10 to 120, more preferably of from 30 to 110,even more preferably of from 35 to 100, and particularly preferably offrom 50 to 100 and most preferably of from 60 to 90. The determinationof the Mooney viscosity is carried out in accordance with ASTM standardD 1646.

They typically have a polydispersity PDI=M_(w)/M_(n) in the range of 1.5to 6 and preferably in the range of 1.8 to 4.

Hydrogenation Conditions:

The hydrogenation is generally carried out at a temperature in the rangefrom 0° C. to 200° C., preferably in the range from 15° C. to 150° C.This means that the process may be carried out at mild conditions. Incase low molecular weight olefins like terminal olefins, internalolefins, cyclic olefins, conjugated olefins, or any other olefins havingat least one carbon-carbon double bond and additionally at least onefurther polar unsaturated double bond are subjected to hydrogenation,the temperature typically lies in the range from 20 to 100° C. In casepolymers with double bonds in the polymer backbone are used assubstrates the hydrogenation temperature typically lies in a range from40 to 200° C., preferably in the range from 70 to 150° C.

The hydrogenation process of the present invention is preferably carriedout with hydrogen gas at a pressure from 0.1 to 20 MPa, preferably at apressure from 1 to 16 MPa. In one embodiment of the present process saidhydrogen gas is essentially pure.

Preferably the hydrogenation process is carried out at a temperature inthe range from 0° C. to 200° C. with hydrogen gas at a pressure from 0.1to 20 MPa, preferably at a temperature in the range from 15° C. to 150°C. with hydrogen gas at a pressure from 1 to 16 MPa.

The amount of catalyst according to general formula (I) can vary in abroad range. Typically the catalyst according to general formula (I) isused in a molar ratio from (0.01-0.20):1, preferably from (0.01-0.05):1based on the substrate to be hydrogenated.

In the hydrogenation of rubber polymers the amount of catalyst accordingto formula (I) may also vary in a broad range. The amount of catalyst isthen calculated on a weight base ratio in “phr” (parts per hundredrubber). Typically 0.005 phr to 2.5 phr catalyst are used based on therubber. Preferably 0.01 phr to 2 phr and more preferably 0.025 phr to 2phr catalyst are used based on the rubber.

The hydrogenation can be carried out in a suitable solvent which doesnot deactivate the catalyst used and also does not adversely affect thereaction in any other way. Preferred solvents include but are notrestricted to methanol, chlorobenzene, bromobenzene, dichloromethane,benzene, toluene, methyl ethyl ketone, acetone, tetrahydrofuran,tetrahydropyran, dioxane and cyclohexane. The particularly preferredsolvent is chlorobenzene. In some cases, when the substrate to behydrogenated itself can function as solvent, e.g. in the case of1-hexene, the addition of a further additional solvent can also beomitted.

According to the present invention the complex catalyst can beintroduced into the polymer by any possible means, such as e.g.mechanical mixing, preferably by using a procedure which can result in ahomogeneous distribution of the catalyst and polymer.

In one embodiment of the present invention the catalyst according toformula (I) is contacted with the substrate to be hydrogenated by addingthe catalyst or catalyst solution to a substrate solution and mixinguntil an efficient distribution and dissolution of the catalyst hastaken place.

The present process can be performed in the presence or absence of anyfurther co-catalyst or other additives. It is not necessary to add suchfurther co-catalyst or other additives. This applies in particular toco-catalysts which are typically used e.g. in combination with otherhydrogenation catalysts known from prior art like the Wilkinson'scatalyst. In one embodiment of the present invention the process isconducted in the presence or absence of co-catalysts having the formulaR¹ _(m)Z, wherein R¹ are identical or different and are each aC₁-C₈-alkyl group, a C₄-C₈-cycloalkyl group, a C₆-C₁₅-aryl group or aC₇-C₁₅-aralkyl group, Z is phosphorus, arsenic, sulphur or a sulphoxidegroup S═O, preferably phosphorus, and m is 2 or 3, preferably 3. In afurther embodiment the present process is conducted in the presence orabsence of triphenylphosphine.

The hydrogenation process of the present invention can be undertaken ina suitable reactor equipped with temperature regulating and agitatingmeans. It is possible to perform the process either batch-wise orcontinuously.

During the course of the hydrogenation reaction of the presentinvention, the hydrogen is added to the reactor. The reaction time istypically from about one quarter of an hour to about 100 hours,depending on operational conditions. As the novel catalysts are robust,it is not necessary to use a special gas dryer to dry the hydrogen.

According to the present invention, when the hydrogenation reaction iscomplete, to the extent desired, the reaction vessel can be cooled (ifapplicable) and vented and the hydrogenated substrate can be isolated byconventional methods well known to any artisan.

Metathesis:

The present invention further provides a process of contacting at leastone substrate containing C═C double bonds with a novel complex catalystaccording to general formula (I) and performing a metathesis reaction.The metathesis reaction can be, for example, a ring-closing metatheses(RCM), a cross-metatheses (CM) or a ring-opening metatheses (ROMP). Forthis purpose, the substrate or substrates to be subjected to themetathesis is/are brought into contact and reacted with the complexcatalyst according to formula (I).

In particular the present invention relates to a process for preparing anitrile rubber with a weight average molecular weight M_(w)′ bysubjecting a starting nitrile rubber having a weight average molecularweight M_(w) to a cross-metathesis reaction in the presence complexaccording to general formula (I), wherein the weight average molecularweight of the starting nitrile rubber M_(w) is higher than the weightaverage molecular weight M_(w) of the nitrile rubber prepared.

In particular the present invention relates to a process for preparing anitrile rubber with a weight average molecular weight M_(w)′ bysubjecting a starting nitrile rubber having a weight average molecularweight M_(w) to a cross-metathesis reaction in the presence complexaccording to general formula (IV), wherein the weight average molecularweight of the starting nitrile rubber M_(w) is higher than the weightaverage molecular weight M_(w) of the nitrile rubber prepared.

Compounds to be Subjected to Metathesis:

Any type of compounds containing at least one C═C double bond can besubjected to a metathesis reaction.

The inventive process can be preferably applied to nitrile rubbers forwhich the definition given above with regard to the hydrogenationreaction shall apply.

The complex catalyst according to general formula (I) is preferably usedfor the metathesis of nitrile rubber. The use according to the inventionis then a process for reducing the molecular weight of nitrile rubber bybringing the nitrile rubber into contact with the catalyst systemaccording to the invention. This reaction is a cross metathesis.

The amount of complex catalyst according to general formula (I) based onthe nitrile rubber used depends on the nature and the catalytic activityof the specific complex catalyst. The amount of complex catalyst used isusually from 1 to 1000 ppm of noble metal, preferably from 2 to 500 ppm,in particular from 5 to 250 ppm, based on the nitrile rubber used.

The NBR metathesis can be carried out in the absence or in the presenceof a coolefin. This is preferably a straight-chain or branchedC₂-C₁₆-olefin. Suitable olefins are, for example, ethylene, propylene,isobutene, styrene, 1-hexene and 1-octene. Preference is given to using1-hexene or 1-octene. If the coolefin is liquid (for example as in thecase of 1-hexene), the amount of coolefin is preferably in the range0.2-20% by weight based on the NBR used. If the coolefin is a gas, forexample as in the case of ethylene, the amount of coolefin is preferablyselected so that a pressure in the range 1×10⁵ Pa-1×10⁷ Pa, preferably apressure in the range from 5.2×10⁵ Pa to 4×10⁶ Pa, is established in thereaction vessel at room temperature.

The metathesis reaction can be carried out in a suitable solvent whichdoes not deactivate the catalyst used and also does not adversely affectthe reaction in any other way. Preferred solvents encompass, but are notrestricted to, dichloromethane, benzene, toluene, methyl ethyl ketone,acetone, tetrahydrofuran, tetrahydropyran, dioxane, cyclohexane andchlorobenzene. The particularly preferred solvent is chlorobenzene. Insome case, when the coolefin itself can act as solvent, e.g. in the caseof 1-hexene, the addition of a further additional solvent can also bedispensed with.

The concentration of the nitrile rubber used in the reaction mixture ofthe metathesis is not critical, but it naturally has to be noted thatthe reaction should not be adversely affected by an excessively highviscosity of the reaction mixture and the mixing problems associatedtherewith. The concentration of the NBR in the reaction mixture ispreferably in the range from 1 to 25% by weight, particularly preferablyin the range from 5 to 20% by weight, based on the total reactionmixture.

The metathetic degradation is usually carried out at a temperature inthe range from 10° C. to 150° C., preferably at a temperature in therange from 20 to 100° C.

The reaction time depends on a number of factors, for example on thetype of NBR, on the type of catalyst, on the catalyst concentrationemployed and on the reaction temperature. The reaction is typicallycomplete within five hours under normal conditions. The progress of themetathesis can be monitored by standard analytical methods, e.g. by GPCmeasurements or by determination of the viscosity.

EXAMPLES

Abbreviations used:

“Grubbs I catalyst” and “Grubbs II catalyst” shall mean

All solvents have been purchased from Caledon Laboratory Chemicals.

I Synthesis of Compounds 1-26 in Accordance with Route B I.1 Synthesisof Ru(PCy₃)(═CHPh)[O(CH₂CH₂S)₂] (1)

A THF solution (5 mL) of (LiSCH₂CH₂)₂O.2THF (0.020 g, 0.137 mmol) wasadded to a THF solution (5 mL) of Grubbs I catalyst (0.100 g, 0.126mmol) and stirred overnight. All volatiles were removed from the darkbrown solution. The dark brown solid was taken up in CH₂Cl₂ (5 mL) andfiltered through a celite packed pipette. Upon concentration to dryness,the resulting dark brown solid was washed with hexane (2×20 mL) anddried to yield a dark red solid (0.075 g, 98%).

¹H NMR (CD₂Cl₂): 13.68 (d, ³J_(PH)=11.8 Hz, 1H, Ru═CH), 7.27 (m, 2H,Ph), 7.14 (m, 3H, Ph), 3.84 (m, 2H, CH₂), 3.21 (m, 2H, CH₂), 2.74 (m,4H, 2×CH₂), 2.11, 1.98, 1.74, 1.61, 1.50, 1.19 (all m, P(C₆H₁₁)₃.

¹³C{¹H} NMR (CD₂Cl₂): 207.95 (Ru═CH), 153.25 (ipso-C, Ph), 128.15 (2×CH,Ph), 125.58 (CH, Ph), 125.39 (2×CH, Ph), 77.96 (2×CH₂), 35.91 (d,¹J_(PC)=24.17 Hz, ipso-C of P(C₆H₁₁)₃), 32.42 (2×CH₂), 29.97 (m-C ofP(C₆H₁₁)₃), 28.31 (d, ²J_(PC)=10.25 Hz, o-C of P(C₆H₁₁)₃), 26.93 (p-C ofP(C₆H₁₁)₃).

³¹P{¹H} NMR (CD₂Cl₂): 65.60.

I.2 Synthesis of Ru(Mes₂Im)(═CHPh)[O(CH₂CH₂S)₂] (2)

Grubbs II catalyst (0.326 g, 0.384 mmol) in CH₃CN (5 mL) was added to(LiSCH₂CH₂)₂O.2THF (0.144 g, 0.489 mmol) in MeCN (5 mL) and toluene (10mL) and stirred for 16 h. All volatiles were removed from the dark brownsolution. CH₂Cl₂ (5 mL) was added to give a dark brown solution whichwas filtered through celite. Upon concentration to dryness, theresulting dark brown solid was washed with hexane (2×20 mL) and dried toyield a black-red solid. X-Ray quality crystals were grown from aCH₂Cl₂/CH₃CN solution. (0.243 g, 99%).

¹H NMR (CD₂Cl₂): 14.85 (s, 1H, Ru═CH), 7.14 (t, 1H, p-H, Ph), 6.97-7.05(m, 4H, Ph), 6.86 (s, 4H, 4×CH, Mes), 3.92 (s, 4H, 2×CH₂, Im), 3.65 (m,2H, CH₂), 2.82 (m, 2H, CH₂), 2.45 (s, 12H, 4×CH₃, Mes), 2.32-2.41 (m,4H, 2×CH₂), 2.23 (s, 6H, 2×CH₃, Mes).

¹³C{¹H} NMR (CD₂Cl₂): 209.98 (Ru═CH), 153.68 (ipso-C, Ph), 137.89(ipso-C, NCN), 137.38 (ipso-C, Mes), 137.31 (ipso-C, Mes), 127.27 (2×CH,Ph), 128.81 (4×CH, Mes), 125.02 (2×CH, Ph), 124.65 (CH, p-C, Ph), 77.56(2×CH₂), 51.84 (2×CH₂, Im), 31.59 (2×CH₂), 20.59 (2×CH₃, Mes), 19.12(4×CH₃, Mes).

I.3 Synthesis of Ru(PCy₃)(═CHPh)Cl[O(CH₂CH₂S)₂BCl₂] (3)

To a CH₂Cl₂ solution (1 mL) of 1 (0.020 g, 0.033 mmol) was added BCl₃ inhexanes (1 M, 33 μL, 0.033 mmol). The red solution immediately turnedgreen. All volatiles were removed, and the resulting dark solid waswashed with CH₃CN (2 mL) and dried to yield a green solid. (0.021 g,89%). X-Ray quality crystals were grown from a CH₂Cl₂/CH₃CN solution.

¹H NMR (CD₂Cl₂): 18.93 (d, ³J_(PH)=11.7 Hz, 1H, Ru═CH), 8.87 (d,³J_(HH)=8.27 Hz, 2H, o-H of C₆H₅), 7.74 (t, ³J_(HH)=7.98 Hz, 1H, p-H ofC₆H₅), 7.51 (t, ³J_(HH)=8.17 Hz, 2H, m-H of C₆H₅), 5.05, 4.56, 4.19,3.82, 3.13, 3.00, 2.89, 2.78 (all m, 1H, CH₂), 2.12, 1.88, 1.82-1.64,1.52, and 1.21-1.13 (all m, P(C₆H₁₁)₃). ¹¹B NMR (CD₂Cl₂): 11.08 (s).

¹³C{¹H} NMR (CD₂Cl₂): 277.37 (Ru═CH), 153.05 (ipso-C, Ph), 132.67 (2×CH,Ph), 131.81 (CH, Ph), 128.36 (2×CH, Ph), 71.15, 68.58 (2×CH₂), 36.20 (d,¹J_(PC)=19.21 Hz, ipso-C of P(C₆H₁₁)₃), 33.24, 30.57 (2×CH₂), 29.54 (m-Cof P(C₆H₁₁)₃), 27.93 (o-C of P(C₆H₁₁)₃), 26.43 (p-C of P(C₆H₁₁)₃).

³¹P{¹H} NMR (CD₂Cl₂): 35.54.

I.4 Synthesis of Ru(Mes₂Im)(═CHPh)Cl[O(CH₂CH₂S)₂BCl₂] (4)

To a CH₂Cl₂ solution (1 mL) of 2 (0.020 g, 0.032 mmol) was added BCl₃ inhexanes (1 M, 32 μL, 0.032 mmol). The brown solution immediately turneddark green. All volatiles were removed, and the resulting dark solid waswashed with CH₃CN (2 mL) and dried to yield a blue-green solid. (0.022g, 92%). X-Ray quality crystals were grown from a CH₂Cl₂/CH₃CN solution.

¹H NMR (CD₂Cl₂): 17.68 (s, 1H, Ru═CH), 8.09 (br, 2H, o-H of C₆H₅) 7.56(t, ³J_(HH)=7.54 Hz, 1H, p-H, Ph), 7.24 (t, ³J_(HH)=7.54 Hz, 2H, m-H ofC₆H₅), 7.03 (s, 2H, 2×CH, Mes), 6.56 (s, 2H, 2×CH, Mes), 4.84 (m, 1H,CH₂), 3.84 (m, 2H, CH₂, Im), 3.74 (m, 1H, CH₂), 3.64 (m, 2H, CH₂, Im),3.01, 2.80, 2.62 (all m, 1H, CH₂), 2.52 (s, 6H, 2×CH₃, Mes), 2.34 (m,2H, CH₂), 2.25 (s, 6H, 2×CH₃, Mes), 2.20 (s, 6H, 2×CH₃, Mes), 2.17 (m,1H, CH₂). ¹³C{¹H} NMR (CD₂Cl₂): 308.91 (Ru═CH), 214.62 (ipso-C, Ph),152.04 (ipso-C, NCN), 138.54 (CMe, Mes), 137.59 (ipso-C, Mes), 137.39(ipso-C, Mes), 132.65 (2×o-CH, Ph), 130.65 (p-CH, Ph), 129.64, 129.25(4×CH, Mes), 126.96 (2×m-CH, Ph), 70.30, 68.12 (2×CH₂), 52.16, 53.83(2×CH₂, Im), 30.56, 26.53 (2×CH₂), 20.70 (2×CH₃, Mes), 19.05 (2×CH₃,Mes), 18.73 (2×CH₃, Mes).

¹¹B NMR (CD₂Cl₂): 11.46.

I.5 Synthesis of [Ru(PCy₃)(═CHPh)[O(CH₂CH₂S)₂BCl₂]CH₃CN]BCl₄ (5)

To a CH₂Cl₂ solution (1 mL) of 3 (0.050 g, 0.069 mmol) was added BCl₃ inhexanes (1 M, 69 μL, 0.069 mmol). The green solution immediately turneddarker green. To this, CH₃CN (0.300 mL) was added and the solutionturned dark red. All volatiles were removed and the dark red solid wasdissolved in CH₂Cl₂ (1 mL) and filtered. Pentane (5 mL) was added and adark red precipitate formed. The solid was collected, washed withpentane (2×2 mL) and dried in vacuo to yield a dark red solid. (0.053 g,87%). X-Ray quality crystals were grown from a CH₂Cl₂ solution layeredwith pentane.

¹¹B NMR (CD₂Cl₂): 11.76 (BS₂Cl₂), 7.00 (BCl₄).

³¹P{¹H} NMR (CD₂Cl₂): 36.14.

I.6 Synthesis of [Ru(Mes₂Im)(═CHPh)[O(CH₂CH₂S)₂BCl₂]CH₃CN]BCl₄ (6)

To a CH₂Cl₂ solution (1 mL) of 4 (0.030 g, 0.040 mmol) was added BCl₃ inhexanes (1 M, 40 μL, 0.040 mmol). The green-blue solution immediatelyturned darker green. To this, CH₃CN (0.100 mL) was added and thesolution turned red. All volatiles were removed and the red solid wasdissolved in CH₂Cl₂ (1 mL) and filtered. Pentane (5 mL) was added and ared precipitate formed. The solid was collected, washed with pentane(2×2 mL) and dried in vacuo to yield a red solid. (0.034 g, 94%). X-Rayquality crystals were grown from a CH₂Cl₂ solution layered with pentane.

¹H NMR (CD₂Cl₂): 17.26 (s, 1H, Ru═CH), 7.64 (m, 3H, o-H and p-H of C₆H₅)7.38 (t, ³J_(HH)=7.99 Hz, 2H, m-H of C₆H₅), 7.00 (s, 2H, 2×CH, Mes),6.77 (s, 2H, 2×CH, Mes), 4.02 (m, 1H, CH₂), 3.83 (br, 5H, 1H, CH₂ and2×CH₂, Im), 3.46 (m, 2H, CH₂, Im), 3.21 (m, 1H, CH₂), 2.66 (m, 3H, 3×CH,CH₂), 2.53 (s, 6H, 2×CH₃, Mes), 2.47 (s, 3H, CH₃CN) 2.27 (s, 6H, 2×CH₃,Mes), 2.25 (s, 6H, 2×CH₃, Mes).

¹³C{¹H} NMR (CD₂Cl₂): 208.50 (ipso-C, Ph), 151.65 (ipso-C, NCN), 140.05(CMe, Mes), 137.53 (ipso-C, Mes), 136.85 (Mes), 136.43 (Mes), 134.08(2×o-CH, Ph), 131.79 (p-CH, Ph) 130.33, 129.92 (4×CH, Mes), 129.06(2×m-CH, Ph), 70.35, 69.45 (2×CH₂), 54.10, 53.14 (2×CH₂, Im), 34.52,33.92 (2×CH₂), 22.76 (2×CH₃, Mes), 19.03 (2×CH₃, Mes), 18.79 (2×CH₃,Mes), 14.20 (CH₃, CH₃CN).

¹¹B NMR (CD₂Cl₂): 11.39 (BS₂Cl₂), 6.92 (BCl₄).

I.6.a Synthesis of [Ru(Mes₂Im)(═CHPh)[O(CH₂CH₂S)₂BCl₂]CH₃CN]O(R³)m (6.a)

To a CH₂Cl₂ solution (3 mL) of 4 (0.300 g, 0.400 mmol) was addedGQ(R³)_(m) (0.410 mmol) as defined below in CH₂Cl₂ (3 ml). To thisexcess CH₃CN was added and the reaction was stirred overnight. The nextmorning the green-blue solution turned to a dark red/purple color. Thesolution was filtered through Celite to remove any KCl salts and thenall volatiles were removed in vacuo. Pentane (5 mL) was added to theresidue and titrated to produce a red precipitate. The solid wascollected, washed with pentane (2×2 mL) and dried in vacuo to yield ared solid.

GQ(R³)_(m)═K[B(C₆F₅)₄]

¹H NMR (CD₂Cl₂): 17.26 (s, 1H, Ru═CH), 7.64 (m, 3H, o-H and p-H of C₆H₅)7.38 (t, ³J_(HH)=7.99 Hz, 2H, m-H of C₆H₅), 7.00 (s, 2H, 2×CH, Mes),6.77 (s, 2H, 2×CH, Mes), 4.02 (m, 1H, CH₂), 3.83 (br, 5H, 1H, CH₂ and2×CH₂, Im), 3.46 (m, 2H, CH₂, Im), 3.21 (m, 1H, CH₂), 2.66 (m, 3H, 3×CH,CH₂), 2.53 (s, 6H, 2×CH₃, Mes), 2.47 (s, 3H, CH₃CN) 2.27 (s, 6H, 2×CH₃,Mes), 2.25 (s, 6H, 2×CH₃, Mes).

¹¹B NMR (CD₂Cl₂): 11.39 (BS₂Cl₂), −11.67 (B(C₆F₅)₄).

GQ(R³)_(m)═K[BPh₄]

¹H NMR (CD₂Cl₂): 17.26 (s, 1H, Ru═CH), 7.64 (m, 3H, o-H and p-H of C₆H₅)7.38 (t, ³J_(HH)=7.99 Hz, 2H, m-H of C₆H₅), 7.24 (m, 8H, BPh₄) 7.00 (s,10H, 2×CH, Mes and BPh₄), 6.77 (s, 6H, 2×CH, Mes and BPh₄), 4.02 (m, 1H,CH₂), 3.83 (br, 5H, 1H, CH₂ and 2×CH₂, Im), 3.46 (m, 2H, CH₂, Im), 3.21(m, 1H, CH₂), 2.66 (m, 3H, 3×CH, CH₂), 2.53 (s, 6H, 2×CH₃, Mes), 2.47(s, 3H, CH₃CN) 2.27 (s, 6H, 2×CH₃, Mes), 2.25 (s, 6H, 2×CH₃, Mes).

¹¹B NMR (CD₂Cl₂): 11.39 (BS₂Cl₂), −6.57 (BPh₄).

GQ(R³)_(m)═K[PF₆]

¹H NMR (CD₂Cl₂): 17.26 (s, 1H, Ru═CH), 7.64 (m, 3H, o-H and p-H of C₆H₅)7.38 (t, ³J_(HH)=7.99 Hz, 2H, m-H of C₆H₅), 7.00 (s, 2H, 2×CH, Mes),6.77 (s, 2H, 2×CH, Mes), 4.02 (m, 1H, CH₂), 3.83 (br, 5H, 1H, CH₂ and2×CH₂, Im), 3.46 (m, 2H, CH₂, Im), 3.21 (m, 1H, CH₂), 2.66 (m, 3H, 3×CH,CH₂), 2.53 (s, 6H, 2×CH₃, Mes), 2.47 (s, 3H, CH₃CN) 2.27 (s, 6H, 2×CH₃,Mes), 2.25 (s, 6H, 2×CH₃, Mes).

¹¹B NMR (CD₂Cl₂): 11.39 (BS₂Cl₂)

³¹P NMR (CD₂Cl₂): −144.48 (hept, ¹J_(PF)=711 Hz, PF₆).

¹⁹F NMR (CD₂Cl₂): −73.01 (hept, ¹J_(PF)=711 Hz, PF₆).

I.7 Synthesis of Ru(PCy₃)(═CHPh)[S(CH₂CH₂S)₂] (7)

A THF solution (5 mL) of (LiSCH₂CH₂)₂S.2THF (0.020 g, 0.123 mmol) wasadded to a THF solution (5 mL) of Grubbs 1 (0.092 g, 0.112 mmol) andstirred overnight. All volatiles were removed from the dark brownsolution. The dark brown solid was taken up in CH₂Cl₂ (5 mL) andfiltered through a celite packed pipette. Upon concentration to dryness,the resulting dark brown solid was washed with hexane (2×20 mL) anddried to yield a dark red solid (0.068 g, 97%). X-ray quality crystalswere grown from a CH₂Cl₂/CH₃CN solution.

¹H NMR (CD₂Cl₂): 13.48 (d, ³J_(PH)=19.3 Hz, 1H, Ru═CH), 7.12 (m, 3H,Ph), 6.93 (m, 2H, Ph), 3.41 (m, 2H, CH₂), 3.24 (m, 2H, CH₂), 2.45 (m,2H, CH₂), 1.93 (m, 2H, CH₂), 2.28, 2.04, 1.73, 1.57, 1.19 (all m,P(C₆H₁₁)₃.

¹³C{¹H} NMR (CD₂Cl₂): 235.16 (d, ²J_(PC)=14.78 Hz, Ru═CH), 157.02(ipso-C, Ph), 127.51 (2×CH, Ph), 125.84 (2×CH, Ph), 125.40 (CH, Ph),45.17 (2×CH₂), 36.28 (2×CH₂), 35.19 (d, ¹J_(PC)=19.78 Hz, ipso-C ofP(C₆H₁₁)₃), 29.98 (m-C of P(C₆H₁₁)₃), 28.37 (d, ²J_(PC)=10.25 Hz, o-C ofP(C₆H₁₁)₃), 26.93 (p-C of P(C₆H₁₁)₃).

³¹P{¹H} NMR (CD₂Cl₂): 41.71.

I.8 Synthesis of Ru(Mes₂Im)(═CHPh)[S(CH₂CH₂S)₂] (8)

A THF solution (5 mL) of (LiSCH₂CH₂)₂S 2THF (0.020 g, 0.123 mmol) wasadded to a THF solution (5 mL) of Grubbs 2 (0.095 g, 0.112 mmol) andstirred overnight. All volatiles were removed from the dark brownsolution. The dark brown solid was taken up in CH₂Cl₂ (5 mL) andfiltered through a celite packed pipette. Upon concentration to dryness,the resulting dark brown solid was washed with hexane (2×20 mL) anddried to yield a dark red solid (0.071 g, 98%). X-ray quality crystalswere grown from a CH₂Cl₂/CH₃CN solution.

¹H NMR (CD₂Cl₂): 14.41 (s, 1H, Ru═CH), 7.19 (t, 1H, p-H, Ph), 7.07 (t,2H, m-H, Ph), 6.88 (d, 2H, o-H, Ph), 6.80 (s, 4H, 4×CH, Mes), 3.99 (s,4H, 2×CH₂, Im), 3.22 (m, 2H, CH₂), 3.00 (m, 2H, CH₂), 2.52 (s, 12H,4×CH₃, Mes), 2.24 (m, 2H, CH₂), 2.19 (s, 6H, 2×CH₃, Mes), 1.73 (m, 2H,CH₂).

¹³C{¹H} NMR (CD₂Cl₂): 211.18 (Ru═CH), 138.08 (ipso-C, Ph), 137.79(ipso-C, NCN), 137.73 (ipso-C, Mes), 129.18 (4×CH, Mes), 127.25.18(2×CH, Ph), 127.11 (2×CH, Ph), 125.14 (CH, p-C, Ph), 52.43 (2×CH₂),44.56 (2×CH₂, Im), 34.77 (2×CH₂), 20.98 (2×CH₃, Mes), 19.68 (4×CH₃,Mes).

I.9 Synthesis of Ru(PCy₃)(═CHPh)Cl[S(CH₂CH₂S)₂BCl₂] (9)

To a CH₂Cl₂ solution (1 mL) of Ru(PCy₃)(═CHPh)[S(CH₂CH₂S)₂] (7) (0.020g, 0.032 mmol) was added BCl₃ in hexanes (1 M, 32 μL, 0.032 mmol). Thered solution immediately turned green. All volatiles were removed, andthe resulting dark solid was washed with CH₃CN (2 mL) and dried to yielda green solid. (0.022 g, 93%).

¹H NMR (CD₂Cl₂): 17.96 (d, ³J_(PH)=15.1 Hz, 1H, Ru═CH), 8.34 (d,³J_(HH)=8.81 Hz, 2H, o-H of C₆H₅), 7.65 (t, ³J_(HH)=7.73 Hz, 1H, p-H ofC₆H₅), 7.40 (t, ³J_(HH)=7.83 Hz, 2H, m-H of C₆H₅), 3.66, 3.13, 2.95 (allm, 1H, CH₂), 2.55 (m, 5H, 5×CH₂), 2.05, 1.88, 1.75-1.45, and 1.18 (allm, P(C₆H₁₁)₃).

¹¹B NMR (CD₂Cl₂): 9.94 (s).

¹³C{¹H} NMR (CD₂Cl₂): 275.25 (Ru═CH), 154.83 (ipso-C, Ph), 132.15 (CH,Ph), 131.84 (2×CH, Ph), 128.77 (2×CH, Ph), 39.32, 38.98 (2×CH₂), 36.73(d, ¹J_(PC)=19.32 Hz, ipso-C of P(C₆H₁₁)₃), 30.24, 30.03 (2×CH₂), 27.79(m-C of P(C₆H₁₁)₃), 27.55 (o-C of P(C₆H₁₁)₃), 26.56 (p-C of P(C₆H₁₁)₃).³¹P{¹H} NMR (CD₂Cl₂): 34.92.

I.10 Synthesis of Ru(Mes₂Im)(═CHPh)Cl[S(CH₂CH₂S)₂BCl₂] (10)

To a CH₂Cl₂ solution (1 mL) of Ru(Mes₂Im)(═CHPh)[S(CH₂CH₂S)₂] (8) (0.020g, 0.031 mmol) was added BCl₃ in hexanes (1 M, 31 μL, 0.031 mmol). Thebrown solution immediately turned dark green. All volatiles wereremoved, and the resulting dark solid was washed with CH₃CN (2 mL) anddried to yield a blue-green solid. (0.022 g, 93%). X-Ray qualitycrystals were grown from a CH₂Cl₂/CH₃CN solution.

¹¹B NMR (CD₂Cl₂): 11.46.

I.11 Synthesis of Ru(PCy₃)(═CHPh)[PhP(CH₂CH₂S)₂] (11)

A THF solution (5 mL) of (LiSCH₂CH₂)₂PPh (0.032 g, 0.134 mmol) was addedto a THF solution (5 mL) of Grubbs 1 (0.100 g, 0.122 mmol) and stirredovernight. All volatiles were removed from the dark brown solution. Thedark brown solid was taken up in CH₂Cl₂ (5 mL) and filtered through acelite packed pipette. Upon concentration to dryness, the resulting darkbrown solid was washed with hexane (2×20 mL) and dried to yield a darkred solid (0.076 g, 89%).

¹H NMR (CD₂Cl₂): 13.31 (dd, ³J_(PH)=23.2 Hz, ³J_(PH)=1.8 Hz, 1H, Ru═CH),7.04 (m, 5H, PPh), 6.94 (d, 2H, Ph), 6.71 (m, 3H, Ph), 3.07 (m, 2H,CH₂), 2.93 (m, 2H, CH₂), 2.47 (m, 5H, CH₂, P(C₆H₁₁)₃), 2.15 (m, 2H,CH₂), 2.20, 1.86, 1.72, 1.33 (all m, P(C₆H₁₁)₃.

¹³C{¹H} NMR (CD₂Cl₂): 235.90 (appt, ²J_(PC)=12.57 Hz, Ru═CH), 155.7 (dd,³J_(PC)=10.50 Hz, 3.85 Hz, ipso-C, Ph), 130.74 (d, ²J_(PC)=9.27 Hz,2×CH, PPh), 128.56 (CH, PPh), 128.55 (d, ¹J_(PC)=267.1 Hz, CH, PPh),127.65 (d, ³J_(PC)=9.25 Hz, 2×CH, PPh), 127.09 (2×CH, Ph), 126.03 (2×CH,Ph), 124.99 (CH, Ph), 34.16 (m, 2×CH₂), 31.49 (m, 2×CH₂), 29.53 (m-C ofP(C₆H₁₁)₃), 28.04 (d, ¹J_(PC)=9.02 Hz, ipso-C of P(C₆H₁₁)₃), 27.70 (d,²J_(PC)=9.02 Hz, o-C of P(C₆H₁₁)₃), 26.56 (p-C of P(C₆H₁₁)₃).

³¹P{¹H} NMR (CD₂Cl₂): 114.7 (d, ²J_(PP)=330.6 Hz), 28.9 (d,²J_(PP)=331.8 Hz).

I.12 Synthesis of Ru(PCy₃)(═CHPh)Cl[PhP(CH₂CH₂S)₂BCl₂] (12)

To a CH₂Cl₂ solution (1 mL) of Ru(PCy₃)(═CHPh)[PhP(CH₂CH₂S)₂] (11)(0.020 g, 0.029 mmol) was added BCl₃ in hexanes (1 M, 29 μL, 0.029mmol). The brown solution immediately turned dark green.

All volatiles were removed, and the resulting dark solid was washed withCH₃CN (2 mL) and dried to yield a dark green solid. (0.022 g, 93%). Thecompound exists as a mixture of isomers (12a, 12b). With the addition ofone more equivalent of BCl₃ the compound becomes an active olefinmetathesis catalyst.

¹H NMR (CD₂Cl₂): 18.06 (d, ³J_(PH)=6.78 Hz, Ru═CH, 12b), 17.32 (dd,³J_(PH)=17.4 Hz, ³J_(PH)=10.6 Hz, Ru═CH, 12a), all other peakscorrespond to isomeric mixture.

¹¹B NMR (CD₂Cl₂): 10.67.

³¹P{¹H} NMR (CD₂Cl₂): 81.54 (d, ²J_(PP)=255.2 Hz, PPh, 12b), 75.76 (d,²J_(PP)=25.8 Hz, PPh, 12a), 29.64 (d, ²J_(PP)=25.9 Hz, PCy₃, 12a), 26.87(d, ²J_(PP)=256.6 Hz, PCy₃, 12b).

I.13 Synthesis of Ru(PCy₃)(═CHPh)[O(C₆H₄S)₂] (13)

A THF solution (5 mL) of (LiSC₆H₄)₂O (0.033 g, 0.134 mmol) was added toa THF solution (5 mL) of Grubbs 1 (0.100 g, 0.122 mmol) and stirredovernight. All volatiles were removed from the dark brown solution. Thedark brown solid was taken up in CH₂Cl₂ (5 mL) and filtered through acelite packed pipette. Upon concentration to dryness, the resulting darkbrown solid was washed with hexane (2×20 mL) and dried to yield a redsolid (0.068 g, 97%). X-ray quality crystals were grown from a CH₂Cl₂solution.

¹H NMR (CD₂Cl₂): 14.69 (d, ³J_(PH)=14.7 Hz, 1H, Ru═CH) 7.48 (d,³J_(HH)=7.6 Hz, 2H, Ph), 7.48 (m, 3H, Ph), 6.90 (m, 4H, Ph), 6.82 (t,³J_(HH)=7.3 Hz, 2H, Ph), 6.72 (m, 2H, Ph), 2.15, 2.02, 1.77, 1.55, 1.19(all m, P(C₆H₁₁)₃.

¹³C{¹H} NMR (CD₂Cl₂): 192.20 (Ru═CH), 154.03 (2×ipso-C, Ph), 152.23(ipso-C, Ph), 139.08 (2×ipso-C, Ph), 132.14 (2×CH, Ph), 130.14 (2×CH,Ph), 127.94 (2×CH, Ph), 126.31 (CH, Ph), 125.27 (2×CH, Ph), 123.97(2×CH, Ph), 122.70 (2×CH, Ph), 115.86 (2×CH, Ph), 35.95 (d,¹J_(PC)=25.05 Hz, ipso-C of P(C₆H₁₁)₃), 31.62 (m-C of P(C₆H₁₁)₃), 30.09(p-C of P(C₆H₁₁)₃), 28.19 (d, ²J_(PC)=10.24 Hz, o-C of P(C₆H₁₁)₃).

³¹P{¹H} NMR (CD₂Cl₂): 68.60.

I.14 Synthesis of Ru(Mes₂Im)(═CHPh)[O(C₆H₄S)₂] (14)

A THF solution (5 mL) of (LiSC₆H₄)₂O (0.038 g, 0.153 mmol) was added toa THF solution (5 mL) of Grubbs II (0.100 g, 0.118 mmol) and stirredovernight. All volatiles were removed from the dark brown solution. Thedark brown solid was taken up in CH₂Cl₂ (5 mL) and filtered through acelite packed pipette. Upon concentration to dryness, the resulting darkbrown solid was washed with hexane (2×20 mL) and dried to yield a redsolid (0.074 g, 86%).

¹H NMR (CD₂Cl₂): 15.60 (s, 1H, Ru═CH), 7.41 (d, 2H, Ph), 6.91 (m, 8H,Ph, Mes), 6.79 (m, 5H, Ph), 6.64 (m, 2H, Ph), 4.08 (s, 4H, 2×CH₂, Im),2.51 (s, 12H, 4×CH₃, Mes), 2.22 (s, 6H, 2×CH₃, Mes).

¹³C{¹H} NMR (CD₂Cl₂): 209.13 (Ru═CH), 153.13 (ipso-C, Ph), 151.45(ipso-C, Ph) 139.53 (ipso-C, NCN), 137.97 (ipso-C, Mes), 137.17 (ipso-C,Mes), 131.26 (2×CH, Ph), 129.18 (2×CH, Ph), 128.90 (2×CH, Ph), 128.14(2×CH, Ph), 126.10 (4×CH, Mes), 127.42 (2×CH, Ph), 125.22 (CH, p-C, Ph),122.90 (CH, Ph), 121.54 (2×CH, Ph), 114.78 (2×CH, Ph), 51.84 (2×CH₂,Im), 20.71 (2×CH₃, Mes), 18.99 (4×CH₃, Mes).

I.15 Synthesis of Ru(PCy₃)(═CHPh)Cl[O(C₆H₄S)₂BCl₂] (15)

To a CH₂Cl₂ solution (1 mL) of Ru(PCy₃)(═CHPh)[O(C₆H₄S)₂] (13) (0.020 g,0.028 mmol) was added BCl₃ in hexanes (1 M, 28 μL, 0.028 mmol). The redsolution immediately turned green and a blue-green precipitate began toform. All volatiles were removed, and the resulting dark solid waswashed with CH₃CN (2 mL) and dried to yield a blue-green solid. (0.020g, 87%).

¹H NMR (CD₂Cl₂): 18.85 (d, ³J_(PH)=11.6 Hz, 1H, Ru═CH), 8.54 (d,³J_(HH)=7.9 Hz, 2H, Ph), 7.74 (m, 3H, Ph), 7.57-7.37 (m, 6H, Ph), 7.20(m, 2H, Ph), 2.40, 2.07, 1.80, 1.62, 1.43 (all m, P(C₆H₁₁)₃.

³¹P{¹H} NMR (CD₂Cl₂): 36.51.

¹¹B NMR (CD₂Cl₂): 12.11.

I.16 Synthesis of Ru(SIMes)(═CHPh)Cl[O(C₆H₄S)₂BCl₂] (16)

To a CH₂Cl₂ solution (1 mL) of Ru(SIMes)(═CHPh)[O(C₆H₄S)₂] (15) (0.020g, 0.027 mmol) was added BCl₃ in hexanes (1 M, 27 μL, 0.027 mmol). Thered solution immediately turned green and a blue-green precipitate beganto form. All volatiles were removed, and the resulting dark solid waswashed with CH₃CN (2 mL) and dried to yield a green solid. (0.019 g,83%).

I.17 Synthesis of [Ru(PCy₃)(═CHPh)[O(C₆H₄S)₂BCl₂]CH₃CN]BCl₄ (17)

To a CH₂Cl₂ solution (1 mL) of 15 (0.020 g, 0.024 mmol) was added BCl₃in hexanes (1 M, 24 μL, 0.024 mmol). The green-blue solution immediatelyturned darker green. To this, CH₃CN (0.100 mL) was added and thesolution turned red. All volatiles were removed and the red solid wasdissolved in CH₂Cl₂ (1 mL) and filtered. Pentane (5 mL) was added and ared precipitate formed. The solid was collected, washed with pentane(2×2 mL) and dried in vacuo to yield a red solid. (0.019 g, 81%).

I.18 Synthesis of [Ru(SIMes)(═CHPh)[O(C₆H₄S)₂BCl₂]CH₃CN]BCl₄ (18)

To a CH₂Cl₂ solution (1 mL) of 15 (0.020 g, 0.024 mmol) was added BCl₃in hexanes (1 M, 24 μL, 0.024 mmol). The green-blue solution immediatelyturned darker green. To this, CH₃CN (0.100 mL) was added and thesolution turned red. All volatiles were removed and the red solid wasdissolved in CH₂Cl₂ (1 mL) and filtered. Pentane (5 mL) was added and ared precipitate formed. The solid was collected, washed with pentane(2×2 mL) and dried in vacuo to yield a red solid. (0.021 g, 88%).

I.19 Synthesis of Ru(PCy₃)(═CHPh)[O(CH₂CH₂O)₂] (19)

A THF solution (5 mL) of (KOCH₂CH₂)₂O (0.025 g, 0.137 mmol) was added toa THF solution (5 mL) of Grubbs 1 (0.100 g, 0.126 mmol) and stirredovernight. All volatiles were removed from the dark brown solution. Thedark brown solid was taken up in toluene (5 mL) and filtered through acelite packed pipette. Upon concentration to dryness, the resulting redsolid was washed with hexane (2×20 mL) and dried to yield a red solid(0.068 g, 90%).

¹H NMR (CD₂Cl₂): 15.72 (d, ³J_(PH)=14.8 Hz, 1H, Ru═CH), 7.91 (d,³J_(HH)=8.02 Hz 2H, Ph), 7.31 (m, 3H, Ph), 4.19 (m, 2H, CH₂), 3.96 (m,2H, CH₂), 3.39 (m, 2H, CH₂), 2.96 (m, 2H, CH₂), 2.44, 2.22, 1.87, 1.67,1.65 (all m, P(C₆H₁₁)₃.

³¹P{¹H} NMR (CD₂Cl₂): 64.76.

I.20 Synthesis of Ru(Mes₂Im)(═CHPh)[O(CH₂CH₂O)₂] (20)

Grubbs 2 (0.100 g, 0.118 mmol) in THF (5 mL) was added to (KOCH₂CH₂)₂O(0.028 g, 0.153 mmol) in THF (10 mL) and stirred for 16 h. All volatileswere removed from the dark brown solution.

Toluene (5 mL) was added to give a dark brown solution which wasfiltered through celite. Upon concentration to dryness, the resultingdark brown solid was washed with hexane (2×20 mL) and dried to yield adark red solid. (0.63 g, 90%).

¹H NMR (CD₂Cl₂): 16.23 (s, 1H, Ru═CH), 7.58 (d, 2H, Ph), 7.18 (m, 3H,Ph), 6.87 (s, 4H, 4×CH, Mes), 3.78 (m, 4H, 2×CH₂), 3.44 (s, 4H, 2×CH₂,Im), 3.18 (m, 4H, 2×CH₂), 2.57 (s, 12H, 4×CH₃, Mes), 2.19 (s, 6H, 2×CH₃,Mes).

I.21 Synthesis of Ru(PCy₃)(═CHPh)Cl[O(CH₂CH₂O)₂BCl₂] (21)

To a CH₂Cl₂ solution (1 mL) of 19 (0.020 g, 0.035 mmol) was added BCl₃in hexanes (1 M, 35 μL, 0.035 mmol). The red solution immediately turnedgreen. All volatiles were removed, and the resulting dark solid waswashed with CH₃CN (2 mL) and dried to yield a green solid. (0.019 g,85%).

I.22 Synthesis of Ru(PCy₃)(═CHPh)Cl[O(CH₂CH₂O)₂BCl₂] (22)

To a CH₂Cl₂ solution (1 mL) of 20 (0.020 g, 0.033 mmol) was added BCl₃in hexanes (1 M, 33 μL, 0.033 mmol). The brown solution immediatelyturned dark green. All volatiles were removed, and the resulting darksolid was washed with CH₃CN (2 mL) and dried to yield a green solid.(0.022 g, 92%).

I.23 Synthesis of [Ru(PCy₃)(═CHPh)[O(CH₂CH₂O)₂BCl₂]CH₃CN]BCl₄ (23)

To a CH₂Cl₂ solution (1 mL) of 3 (0.020 g, 0.031 mmol) was added BCl₃ inhexanes (1 M, 31 μL, 0.031 mmol). The green solution immediately turneddarker green. To this, CH₃CN (0.300 mL) was added and the solutionturned dark red. All volatiles were removed and the dark red solid wasdissolved in CH₂Cl₂ (1 mL) and filtered. Pentane (5 mL) was added and adark red precipitate formed. The solid was collected, washed withpentane (2×2 mL) and dried in vacuo to yield a dark red solid. (0.022 g,85%).

I.24 Synthesis of [Ru(Mes₂Im)(═CHPh)[O(CH₂CH₂O)₂BCl₂]CH₃CN]BCl₄ (24)

To a CH₂Cl₂ solution (1 mL) of 4 (0.030 g, 0.042 mmol) was added BCl₃ inhexanes (1 M, 42 μL, 0.042 mmol). The green-blue solution immediatelyturned darker green. To this, CH₃CN (0.100 mL) was added and thesolution turned red. All volatiles were removed and the red solid wasdissolved in CH₂Cl₂ (1 mL) and filtered. Pentane (5 mL) was added and ared precipitate formed. The solid was collected, washed with pentane(2×2 mL) and dried in vacuo to yield a red solid. (0.032 g, 84%).

I.25 Synthesis of Ru(PCy₃)(═CHPh)Cl[O(CH₂CH₂S)₂B(C₆F₅)₂] (25)

To a CH₂Cl₂ solution (0.5 mL) of 1 (0.020 g, 0.033 mmol) was addedCH₂Cl₂ solution (0.5 mL) of ClB(C₆F₅)₂ (0.013 g, 0.033 mmol). The redsolution immediately turned green. All volatiles were removed, and theresulting dark solid was washed with CH₃CN (2 mL) and dried to yield agreen solid. (0.024 g, 75%).

¹H NMR (CD₂Cl₂): 18.47 (d, ³J_(PH)=13.9 Hz, 1H, Ru═CH), 8.18 (br, 2H,o-H of C₆H₅), 7.53 (t, ³J_(HH)=7.18 Hz, 1H, p-H of C₆H₅), 7.24 (t,³J_(HH)=7.18 Hz, 2H, m-H of C₆H₅), 5.05, 4.78, (m, 2×1H, CH₂), 4.28 (m,2H, CH₂), 2.93, 2.64, 2.52, 2.39 (all m, 1H, CH₂), 1.88, 1.65,1.45-1.33, 1.14 (all m, P(C₆H₁₁)₃). ¹¹B NMR (CD₂Cl₂): 5.20 (s).

¹⁹F NMR (CD₂Cl₂): −155.7, −157.1, −164.0.

I.26 Synthesis of Ru(PCy₃)(═CHPh)Cl[O(CH₂CH₂S)₂B(C₆F₅)₂] (26)

To a CH₂Cl₂ solution (1 mL) of 2 (0.020 g, 0.032 mmol) was added CH₂Cl₂solution (0.5 mL) of ClB(C₆F₅)₂ (0.012 g, 0.032 mmol). The brownsolution immediately turned dark green. All volatiles were removed, andthe resulting dark solid was washed with CH₃CN (2 mL) and dried to yielda blue-green solid. (0.028 g, 87%).

¹H NMR (CD₂Cl₂): 17.75 (s, 1H, Ru═CH), 7.65 (br, 2H, o-H of C₆H₅) 7.43(t, ³J_(HH)=7.31 Hz, 1H, p-H, Ph), 7.07 (t, ³J_(HH)=7.31 Hz, 2H, m-H ofC₆H₅), 7.05 (s, 2H, 2×CH, Mes), 6.60 (s, 2H, 2×CH, Mes), 4.95 (m, 1H,CH₂), 3.81 (m, 4H, CH₂, Im, 2×CH₂), 3.64 (m, 2H, CH₂, Im), 2.79, 2.69,2.62 (all m, 1H, CH₂), 2.56 (s, 6H, 2×CH₃, Mes), 2.49 (m, 1H, CH₂), 2.26(s, 6H, 2×CH₃, Mes), 2.19 (s, 6H, 2×CH₃, Mes), 2.00 (m, 1H, CH₂).

¹¹B NMR (CD₂Cl₂): 8.86.

I.27 Synthesis of [Ru(Mes₂Im)(═CHPh)[O(CH₂CH₂S)₂BCl₂]]BCl₄ (4+BCl₃)

To a CH₂Cl₂ solution (1 mL) of 4 (0.030 g, 0.040 mmol) was added BCl₃ inhexanes (1 M, 40 μL, 0.040 mmol). The green-blue solution immediatelyturned darker green. This solution of 4+BCl₃ can be used for catalysis.

I.28 Synthesis of [Ru(PCy₃)(═CHPh)[O(CH₂CH₂O)₂BCl₂]]BCl₄ (22+BCl₃)

To a CH₂Cl₂ solution (1 mL) of 4 (0.030 g, 0.042 mmol) was added BCl₃ inhexanes (1 M, 42 μL, 0.042 mmol). The green-blue solution immediatelyturned darker green. This solution of 22+BCl₃ can be used for catalysis.

I.29 Synthesis of [Ru(SIMes)(═CHPh)[O(C₆H₄S)₂BCl₂]]BCl₄ (16+BCl₃)

To a CH₂Cl₂ solution (1 mL) of 15 (0.020 g, 0.024 mmol) was added BCl₃in hexanes (1 M, 24 μL, 0.024 mmol). The green-blue solution immediatelyturned darker green. This solution of 16+BCl₃ can be used for catalysis.

II Synthesis of Transition Metal Complexes Via Route A

In the following synthesis route A is described to prepare compounds ofgeneral formula (I) in accordance with the present invention usingthioacetals as one starting material.

All thioacetals were prepared modifying a procedure disclosed in J.Chem. Soc., Perkin Trans. 1, 1994, 707-715 (Hu Xianming, Richard M.Kellogg, Fre van Bolhuis) as outlined in the following:

II.1 Synthesis of Thioacetals

A solution of p-toluenesulfonic acid (5 mg) (“TsOH”) in 200 mL of MeOHwas heated to 55° C. in a 3-neck round bottom flask fitted with acondenser, addition funnel and septum. A solution of 2-Mercaptoethylether (1.065 g, 7.7 mmol) and benzaldehyde (0.817 g, 7.7 mmol) in 150 mLMeOH was added drop wise from the addition funnel over 4 hours. Themixture was left at 55° C. overnight. All volatiles were removed and thewhite solid was dissolved in 10 mL of toluene. The solution was ranthrough an alumina plug and all volatiles were removed from thefiltrate. The thioacetal (27) was crystallized from CH₂Cl₂ and obtainedas colorless needles. (1.65 g, 95%).

¹H NMR (C₆D₆): 7.22 (s, 2H, Ph), 6.84 (t, 2H, Ph), 6.75 (t, 1H, Ph),5.80 (s, 1H, CH), 3.50 (m, 2H, CH₂), 2.90 (m, 2H, CH₂), 2.50 (m, 2H,CH₂), 2.05 (m, 2H, CH₂).

A similar procedure was used for the synthesis of all thioacetals likee.g.

II.2 Synthesis of Compound (1)

To a C₆H₆ (1 mL) solution of Ru(PPh₃)₃(H)₂ (20 mg, 0.0174 mmol) wasadded PCy₃ (6 mg, 0.0214 mmol) and the thioacetal (27) (5 mg, 0.0221mmol). The mixture was heated at 50° C. in an oil bath for 2 hr and theyellow solution turned dark red as bubbles were evolved. Pentane wasadded to the solution to crash out the red product which was washed withpentane. Spectral data match that of compound (1) previously reported.

II.3 Synthesis of Compound (2)

To a C₆H₆ (1 mL) solution of Ru(PPh₃)₃(H)₂ (20 mg, 0.0174 mmol) wasadded the thioacetal (27) (5 mg, 0.0221 mmol). The mixture was heated at50° C. in an oil bath for 2 hr and the yellow solution turned dark redas bubbles were evolved. SIMes (6 mg, 0.0195 mmol) was added to thesolution and the mixture was heated at 50° C. for another hour. Pentanewas added to the solution to crash out the red product which was washedwith pentane. Spectral data match that of compound (2) previouslyreported.

II.3a Synthesis of Compound (2)

Ru(PPh₃)₃HCl (0.100 g, 0.108 mmol), thioacetal 27 (0.030 g, 0.130 mmol)and were dissolved in THF (5 mL) and toluene (5 mL) under N₂. Thesolution was cooled to −78° C. and n-BuLi (0.068 mL, 1.6 M in hexanes)was added dropwise. The reaction mixture was stirred at −78° C. for 2 hand then allowed to warm to room temperature. After stirring at roomtemperature for another 2 h SIMes (0.050 g, 0.162 mmol) was added to thereaction mixture. The solution was then heated to 60° C. for 3 h. Thesolvent was removed and the resulting brown solid was dissolved intoluene (10 mL) and filtered through a plug of celite. The filtrate wasconcentrated and hexanes (20 mL) was added to precipitate 2 which wascollected by filtration and washed with hexanes (3×5 mL) to give a redsolid. All spectral data matched that of compound (2).

II.3b Synthesis of Compound (2)

SIMes was stirred with Ru(PCy₃)₂(H₂)HCl in toluene for 2 h. The solutionwas cooled to −78° C. and n-BuLi was added dropwise. The mixture wasstirred for 2 h and allowed to warm to room temperature and stirred for2 h more. Compound (2) was isolated in an identical fashion to theprocedure described in II.3a.

II.4 Synthesis of Compound (8)

An identical synthetic procedure as the synthesis of compound (2) fromRu(PPh₃)₃H₂ was used to give compound (8).

II.5 Synthesis of Compound (14)

An identical synthetic procedure as used for the synthesis of complex(2) from Ru(PPh₃)₃H₂ was used to give compound (14).

II.6 Synthesis of Compound (1)

Ru(cod)(cot) (20 mg, 0.063 mmol), PCy₃ (20 g, 0.070 mmol) and thioacetal27 (14 g, 0.063 mmol) were mixed and heated in C₆H₆ at 50° C. for 2 hr.The solution was cooled to room temperature and the solvent was removedin vacu. The resulting solid was washed with hexanes and dried in vacuto give 1 as a red solid.

II.6a Synthesis of Compound (1)

Ru(PPh₃)₃HCl (0.100 g, 0.108 mmol), thioacetal 27 (0.030 g, 0.130 mmol)and PCy₃ (0.045 g, 0.162 mmol) were dissolved in THF (5 mL) and toluene(5 mL) under N₂. The solution was cooled to −78° C. and n-BuLi (0.068mL, 1.6 M in hexanes) was added dropwise. The reaction mixture wasstirred at −78° C. for 2 h and then allowed to warm to room temperature.After stirring at room temperature for another 2 h the solvent waspumped off. The resulting brown solid was dissolved in toluene (10 mL)and filtered through a plug of celite. The filtrate was concentrated andhexanes (20 mL) was added to precipitate 1 which was collected byfiltration and washed with hexanes (3×5 mL) to give a red solid. Allspectral data matched that of compound 1.

II.6b Synthesis of Compound (1)

Analog to the process described in II.6a, Ru(PCy₃)₂(H₂)HCl can be usedas the metal source without the addition of PCy₃.

II.7 Synthesis of Compound 31

An identical synthetic procedure as the synthesis of Compound (2) fromRu(PPh₃)₃H₂ was used to give compound (31).

III Catalysis Experiments III.1 Metathesis Reactions Using Compounds(2), (4), and (4)+BCl₃

III.1.1 Ring Closing Metathesis of Diethyl Diallyl Malonate

A standard procedure for the ring closing metathesis of diethyl diallylmalonate is as follows. The required amount of catalyst (5 mol %) wasweighed out and dissolved in CD₂Cl₂. For the tests involving 4 with theaddition of another equivalent of BCl₃ the required volume was added andthe mixture allowed to stand for 5 min. The solutions were placed in anNMR tube equipped with a septa. Diethyl allyl malonate (40 μL, 0.165mmol) was added via the septum and solution was mixed. Reaction progresswas monitored by ¹H NMR every 2 min. Reaction progress was determined byintegration of the olefinic peaks of the starting material versus theproduct. The results as listed in Table 1 are graphically shown in FIG.1.

TABLE 1 Ring Closing Metathesis of diethyl diallyl malonate Time ConvNMR (min) (%) Compound (2) 1 5 0 2 7 0 3 9 0 4 11 0.1 5 13 0.1 6 15 0.17 17 0.2 8 19 0.2 9 21 0.2 10 23 0.3 11 25 0.3 12 27 0.3 13 29 0.4 14 310.4 15 33 0.4 16 35 0.5 17 37 0.5 18 39 0.6 19 41 0.7 20 43 0.7 Compound(4) 1 5 0 2 7 0 3 9 0 4 11 0 5 13 0.3 6 15 0.4 7 17 0.5 8 19 0.6 9 210.6 10 23 0.7 11 25 0.7 12 27 0.8 13 29 0.9 14 31 0.9 15 33 1 16 35 1.117 37 1.2 18 39 1.3 19 41 1.4 20 43 1.4 Compound (4) + BCl₃ 1 5 55.8 2 767.5 3 9 75.4 4 11 81.1 5 13 85.1 6 15 88.2 7 17 90.7 8 19 92.4 9 2193.7 10 23 94.8 11 25 95.9 12 27 96.4 13 29 97 14 31 97.4 15 33 97.8 1635 98.1 17 37 98.2 18 39 98.4 19 41 98.6 20 43 98.6

III.1.2 Ring Opening Polymerization of 1,5-cyclooctadiene

A standard procedure for the ring opening polymerization of1,5-cyclooctadiene is as follows. Standard solutions in CD₂Cl₂ wereprepared and the appropriate volumes (0.1 mol %) were diluted for thetests. For tests involving 4 with the addition of another equivalent ofBCl₃ the required volume was added and the mixture allowed to stand for5 min. The solutions were placed in an NMR tube equipped with a septa.1,5-cyclooctadiene (50 μL, 0.40 mmol) was added via the septum andsolution was mixed. Reaction progress was monitored by ¹H NMR every 2min. Reaction progress was determined by integration of the peaks of thestarting material versus the product. The results as listed in Table 2are graphically shown in FIG. 2.

TABLE 2 Ring Opening Polymerization of 1,5-cyclooctadiene Time Conv NMR(min) (%) Compound 2 1 2 1.1 2 4 2.4 3 6 3.5 4 8 4.6 5 10 5.7 6 12 6.8 714 7.9 8 16 8.9 9 18 10 10 20 11.4 11 22 12.4 12 24 13.6 13 26 14.8 1428 16.1 15 30 17.3 16 32 18.5 17 34 19.7 18 36 21 19 38 22.1 20 40 23.521 42 24.7 22 44 25.9 Compound 4 1 2 1.1 2 4 1.6 3 6 2 4 8 2.3 5 10 2.56 12 2.7 7 14 2.9 8 16 3.1 9 18 3.2 10 20 3.3 11 22 3.6 12 24 3.8 13 263.8 14 28 3.9 15 30 4.1 16 32 4.2 17 34 4.4 18 36 4.5 19 38 4.6 20 404.7 21 42 4.8 22 44 4.8 Compound 4 + BCl₃ 1 2 17.3 2 4 30.9 3 6 36.5 4 839.8 5 10 41.7 6 12 43.4 7 14 44.7 8 16 45.7 9 18 46.7 10 20 47.4 11 2248.2 12 24 48.9 13 26 49.4 14 28 49.9 15 30 50.4 16 32 50.8 17 34 51.118 36 51.5 19 38 52 20 40 52.3 21 42 52.8 22 44 53.1

III.1.3 Cross Metathesis of 5-hexenyl acetate and methyl methacrylate

A standard procedure for cross metathesis of 5-hexenyl acetate andmethyl methacrylate is as follows. The required amount of catalyst (5mol %) was weighed out and dissolved in CD₂Cl₂. For the tests involving4 with the addition of another equivalent of BCl₃ the required volumewas added and the mixture allowed to stand for 5 min. The solutions wereplaced in an NMR tube equipped with a septa. A mixture of 5-hexenylacetate (20 μL, 0.12 mmol) and methyl methacrylate (10 μL, 0.11 mmol)was added via the septum and solution was mixed. Reaction progress wasmonitored by ¹H NMR every 2 min. Reaction progress was determined byintegration of the olefinic peaks of the starting material versus theproduct. The results as listed in Table 3 are graphically shown in FIG.3.

TABLE 3 Cross Metathesis of 5-hexenyl acetate and methyl methacrylateTime Conv NMR (min) (%) Compound (2) 1 2 0 2 4 0 3 6 0 4 8 0 5 10 0 6 120 7 14 0 8 16 0 9 18 0 10 20 0 11 22 0 12 24 0 13 26 0 14 28 0 15 30 016 32 0 17 34 0 18 36 0 19 38 0 20 40 0 30 60 0 40 80 0 50 100 0 60 1200 70 140 0 80 160 0 90 180 0 Compound (4) 1 2 0 2 4 0 3 6 0 4 8 0 5 10 06 12 0 7 14 0 8 16 0 9 18 0 10 20 0 11 22 0 12 24 0 13 26 0 14 28 0 1530 0 16 32 0 17 34 0 18 36 0 19 38 0 20 40 0 30 60 0 40 80 0 50 100 0 60120 0 70 140 0 80 160 0 90 180 0 Compound (4) + BCl₃ 1 2 30.9 2 4 40.4 36 45.6 4 8 48.2 5 10 50.2 6 12 51.9 7 14 52.4 8 16 53.7 9 18 53.7 10 2054.2 11 22 54.9 12 24 55.2 13 26 55.6 14 28 56.7 15 30 56.8 16 32 57.417 34 57.5 18 36 57.8 19 38 57.9 20 40 58.1 30 60 59.2 40 80 60.4 50 10060.7 60 120 60.9 70 140 61.7 80 160 62 90 180 62.3

III.2 Standard Metathesis Reactions with Compound (22)+BCl₃

III.2.1 Ring Closing Metathesis of Diethyl Diallyl Malonate

The results as listed in the following Table 4 are graphically shown inFIG. 4.

TABLE 4 Use of catalyst compound (22) + BCl₃ in ring closing metathesisof diethyl diallyl malonate with either 5 mol % of catalyst (Trial A) or1 mol % catalyst (Trial B) Trial A Trial B Time Conversion Conversion(min) (%) (%) 2 24 3.7 4 67 10.3 6 93 15.7 8 100 20.3 10 24.1 12 28.0 1431.2 16 34.1 18 36.8 20 39.4 22 41.8 24 43.8 26 45.7 28 47.4 30 49.1 3250.5 34 52.2 36 53.5 38 55.0 40 55.9

III.2.2 Ring Opening Polymerization of 1,5-cyclooctadiene

The results as listed in the following Table 5 are graphically shown inFIG. 5.

TABLE 5 Use of catalyst compound (22) + BCl₃ in ring openingpolymerization of 1,5-cyclooctadiene Time Conv (min) (%) 2 11.5 4 56.5 674.3 8 82.1 10 86.2 12 87.6 14 88.9 16 90.5 18 91.1 20 92.9 22 93.5 2494.1 26 94.9 28 95.3 30 95.6 32 95.8

III.2.3 Cross Metathesis of 5-hexenyl acetate and methyl methacrylate

The results as listed in the following Table 6 are graphically shown inFIG. 6.

TABLE 6 Use of catalyst compound 22 + BCl₃ in cross metathesis of5-hexenyl acetate and methyl methacrylate Time Conv (min) (%) 10 19.2 2022.2 30 26.1 40 27.4 60 28.6 80 29.4 100 30.5 120 30.8 140 31 160 31.3180 31.5

III.3 Standard Metathesis Reactions with Compound (16)+BCl₃

III.3.1 Ring Closing Metathesis of Diethyl Diallyl Malonate

The results as listed in the following Table 7 are graphically shown inFIG. 7.

TABLE 7 Ring Closing Metathesis of diethyl diallyl malonate 16 + BCl3Time Conv (min) (%) 2 5.7 4 12.6 6 15.3 8 17.5 10 19.7 12 21.2 14 23.416 25.3 18 26.7 20 27.5 22 29.3 24 30.4 26 31.3 28 32.2 30 32.8 32 33.634 33.8 36 34.6 38 35.2 40 35.9

III.4 Cross Metathesis of Nitrile Butadiene Rubber (NBR) and 1-hexene

A standard procedure for the cross metathesis of nitrile butadienerubber (NBR) and 1-hexene is as follows. 75 g of NBR was placed in 325 gof chlorobenzene and placed on a shaker for 48 hr to give a 15 wt % NBRsolution. 1-hexene (4 g) was added to the solution and shaken for 1 hr.The catalysts were prepared by dissolving the required mass of compound(4) in CH₂Cl₂ (5 mL) in a glove box and 1 equivalent of BCl₃ was added.The solutions were stirred for 5 min before being taken out of the glovebox and added to the NBR solutions. Samples were taken at 1, 2, 3, 4,and 24 hr. All volatiles were removed from the samples and the Mn, Mw,and PDI were determined by GPC using a polystyrene calibration curve.

All molecular weights Mw (weight average molecular weight) and Mn(number average molecular weight) are hereinafter given in g/mol. “PDI”means polydispersity index.

TABLE 8 NBR before metathesis NBR Mw 270,500 Mn 95,500 PDI 2.83

III.4.1 Cross Metathesis Using Compound (4)+BCl₃

The cross-metathesis using compound (4)+BCl₃ in the amounts mentioned inTable 9 or in comparison Grubbs II catalyst was performed according tothe above mentioned standard procedure. The results as listed in thefollowing Table 9.

TABLE 9 Cross metathesis of nitrile butadiene rubber (NBR) and 1-hexeneusing compound (4) + BCl₃ (inventive) and Grubbs II catalyst(comparison) Inventive Inventive Comparison example example Example 37.5mg 75 mg 5 mg Catalyst compound compound Grubbs II loading (4) + BCl₃(4) + BCl₃ catalyst Reaction time: 24 hr Mw 154,500 97,000 164,000 Mn67,350 47,850 69,200 PDI 2.29 2.03 2.37

III.4.2 Cross Metathesis Using Compound (6)

The cross-metathesis using compound (6) with a catalyst loading of 37.5mg was performed according to the above mentioned standard procedure.The results as listed in the following Table 10.

TABLE 10 Cross metathesis of nitrile butadiene rubber (NBR) and 1-hexeneusing compound (6) (inventive) Reaction time 1 hr 2 hr 3 hr 24 hr Mw225,000 243,000 255,500 199,500 Mn 86,000 88,800 94,500 81,000 PDI 2.622.74 2.70 2.46

III.4.3 Cross Metathesis Using Compound (22)+BCl₃

The cross-metathesis using compound (22)+BCl₃ with a catalyst loading of37.5 mg was performed according to the above mentioned standardprocedure. The results as listed in the following Table 11.

TABLE 11 Cross metathesis of nitrile butadiene rubber (NBR) and 1-hexeneusing compound (22) + BCl₃ (inventive) and Grubbs II catalyst(comparison) Inventive example Comparison Example Catalyst 37.5 mg 5 mgloading compound 4 + BCl₃ Grubbs 11 catalyst Reaction time: 0.25 hr Mw156500 Mn 63500 PDI 2.464567 Reaction time: 24 hr Mw 160,000 164,000 Mn63,400 69,200 PDI 2.52 2.37

III.5 Hydrogenation of NBR

A standard procedure for the hydrogenation of NBR is as follows. A 5 mol% solution of NBR in chlorobenzene was prepared. In a glovebox 2 mL ofthe NBR solution was place in a vial with a stirbar. The catalystsolution was added to the NBR and the vials were placed in a highpressure Parr reactor. The reactor was purged with H₂ and charged to therequired pressure. The reactor was heated to the required temperatureand the reaction was left for 20 hr. The degree of hydrogenation wasdetermined by IR spectroscopy.

TABLE 11 Hydrogenation of NBR with compounds (2), (20), (22), and (22) +BCl₃ Loading Pressure Degree of Catalyst (μmol) (bar) Hydrogenation  2(comparison) 10 50 82.4* 5 82 71.3* 20 (comparison) 10 50 Crosslinking 582 Crosslinking 22 (inventive) 10 50 73.7 10 82 99 22 + BCl₃ 10 50 36.4(inventive) 10 82 98 *with Crosslinking

The invention claimed is:
 1. A complex having general formula (I)

wherein M means Ru, Os or Fe; X means O or S; D means S, O, PR², or NR²with R² meaning straight chain or branched C₁-C₁₄ alkyl, C₃-C₈cycloalkyl, or C₆-C₂₄ aryl; Y means a divalent moiety or anunsubstituted or substituted C₆-C₁₀ arylene group; R means unsubstitutedor substituted C₆-C₁₄ aryl; L¹ means a ligand; Z means B, Al, Ga, or In;R¹ are identical or different and represent F, Cl, Br, I, unsubstitutedor substituted, straight chain or branched C₁-C₁₄ alkyl, C₃-C₈cycloalkyl, or unsubstituted or substituted C₆-C₂₄ aryl; X¹ means F, Cl,Br, or I L² is a two electron donor ligand; and n Is either 0 or
 1. 2.The complex according to claim 1, wherein in general formula (I) M meansRu X means O or S; D means S, O, PR², or NR² with R² meaning straightchain or branched C₁-C₆ alkyl, C₅-C₆ cycloakyl, or C₆-C₁₄ aryl Y means adivalent moiety or an unsubstituted or substituted C₆-C₁₀ arylene group;R means unsubstituted or substituted C₆-C₁₄ aryl; L¹ means either P(R²)₃wherein R² are identical or different and mean straight chain orbranched C₁-C₈ alkyl, C₆-C₁₄ aryl, or C₃-C₁₀ cycloalkyl, wherein each ofthe aforementioned groups may be substituted by one or more substituentsselected from the group consisting of halogen, SO₃Na, C₁-C₈-alkyl, thelatter either unsubstituted or substituted by one or more F, Cl, Br orI, C₆-C₁₄ aryl, and C₁-C₅-alkoxy; or an N-heterocyclic carbene ligand ofgeneral formulae (IM-a) or (IM-b)

wherein R⁴, R⁵, R⁶, R⁷ are identical or different and are each hydrogen,straight-chain or branched C₁-C₃₀-alkyl, C₃-C₂₀-cycloakyl,C₂-C₂₀-alkenyl, C₂-C₂₀-alkynyl, C₆-C₄-aryl, C₁-C₂₀-carboxylate,C₁-C₂₀-alkoxy, C₂-C₂₀-alkenyloxy, C₂-C₂₀-alkynyloxy, C₆-C₂₀-aryloxy,C₂-C₂₀-alkoxycarbonyl, C₁-C₂₀-alkylthio, C₆-C₂₀-arylthio,C₁-C₂₀-alkylsulphonyl, C₁-C₂₀-alkylsulphonate, C₆-C₂₀-arylsulphonate orC₁-C₂₀-alkylsulphinyl; or in the alternative R⁶ and R⁷ have the abovementioned meanings and at the same time R⁴ and R⁵ jointly form a C₆-C₁₀cyclic structure together with the two adjacent carbon atoms in theimidazoline or imidazolidine ring; Z means B, Al, Ga, or In; R¹ areidentical or different and represent F, Cl, Br, I, unsubstituted orsubstituted, straight chain or branched C₁-C₁₄ alkyl, C₃-C₈ cycloalkyl,or unsubstituted or substituted C₆-C₂₄ aryl; X¹ means F, Cl, Br, or I L²is a two electron donor ligand; and n is either 0 or
 1. 3. The complexaccording to claim 1, wherein in general formula (I) M means Ru; X meansO or S; D means S, O, PR², or NR² with R² meaning straight chain orbranched C₁-C₆ alkyl, C₅-C₆ cycloalkyl, or C₆-C₁₄ aryl Y means1,2-ethylene or 1,2-phenylene; R means phenyl with none, 1, 2, 3, 4, or5 substituents selected from the group consisting of F, Cl, Br, and I;L¹ is selected from the group consisting of PPh₃, P(p-Tol)₃, P(o-Tol)₃,PPh(CH₃)₂, P(CF₃)₃, P(p-FC₆H₄)₃, P(p-CF₃C₆H₄)₃, P(C₆H₄—SO₃Na)₃,P(CH₂C₆H₄—SO₃Na)₃, P(isopropyl)₃, P(CH(CH₃)CH₂CH₃)₃, P(cyclopentyl)₃,P(cyclohexyl)₃, P(neopentyl)₃, P(neophyl)₃, and an N-heterocycliccarbene ligand of general formulae (IM-a) or (IM-b), wherein R⁵ and R⁷are identical or different and represent i-propyl, neopentyl, adamantyl,mesityl or 2,6-diisopropylphenyl, and R⁴ and R⁵ are identical ordifferent and represent hydrogen, C₆-C₂₄-aryl, straight-chain orbranched C₁-C₁₀-alkyl, or together with the carbon atoms to which theyare bound form a C₆-C₁₀ cycloalkyl or C₆-C₁₀ aryl substituent; Z meansB, Al, Ga, or In; R¹ are identical or different and represent F, Cl, Br,or I; X¹ means F, Cl, Br, or I; L represents CH₃CN, pyrdine ortetrahydrofuran; and n is either 0 or
 1. 4. The complex according toclaim 1, wherein in formula (I) M means Ru X means O or S; D means S, O,PR², or NR² with R² meaning straight chain or branched C₁-C₆ alkyl,C₅-C₆ cycloalkyl, or C₅-C₁₄ aryl Y means 1,2-ethylene or 1,2-phenylene;R means phenyl with none or 5 substituents selected from the groupconsisting of F, Cl, Br, and I; L¹ is selected from the group consistingof PPh₃, P(p-To)₃, P(o-Tol)₃, PPh(CH₃), P(CF₃)₃, P(p-FC₆H₄)₃,P(P—CF₃C₆H₄)₃, P(C₆H₄—SO₃Na)₃, P(CH₂C₆H₄—SO₃Na)₃, P(isopropyl)₃,P(CH(CH₃)CH₂CH₃)₃, P(cyclopentyl)₃, P(cyclohexyl)₃, P(neopentyl)₃,P(neophyl)₃, and N-heterocyclic carbene ligands of the structures(VIII-a) to (VIII-o)

Z means B; R¹ are identical and represent Cl; X¹ means Cl; L² representsCH₃CN, pyridine or tetrahydrofuran; and n is either 0 or
 1. 5. A processfor preparing the complex according to claim 1, the process comprising:(1) reacting a complex of general formula (II)

wherein M means Ru, Os or Fe; X means O or S; D means S, O, PR, or NR²with R² meaning straight chain or branched C₁-C₁₄ alkyl, C₃-C₈cycloalkyl, or C₆-C₂₄ aryl, Y means a divalent moiety or anunsubstituted or substituted C₆-C₁₀ arylene group; R means unsubstitutedor substituted C₆-C₁₄ aryl; L¹ means a ligand; with a compound ofgeneral formula (III)ZX¹(R¹)₂  (III) wherein Z means B, Al, Ga or In; X¹ means F, Cl, Br, orI; and R¹ are identical or different and represent F, Cl, Br, I,unsubstituted or substituted, straight chain or branched C₁-C₁₄-alkyl,C₃-C₈ cycloalkyl, or unsubstituted or substituted C₆-C₂₄ aryl; resultingin a complex according to general formula (IV)

and (2) reacting the compound of general formula (IV) with a compound ofgeneral formula (V)Z(R¹)₃  (V) to obtain the complex catalyst according to general formula(I).
 6. The process according to claim 5, further including, to obtaincomplex catalyst according to general formula (I) with n being 1, addingthe ligand L² simultaneously with or after addition of the compound ofgeneral formula (V) in step
 2. 7. The process according to claim 5,wherein: M means Ru, Os or Fe; X means O or S; D means S, O, PR², or NR²with R² meaning straight chain or branched C₁-C₆ alkyl, C₅-C₆cycloalkyl, or phenylene; Y means 1,2-ethylene, 1,3-propylene,1,4-butylene, 1,2-phenylene, or 2,3-naphthylene; R means phenyl withnone, 1, 2, 3, 4, or 5 substituents selected from the group consistingof F, Cl, Br, and I; L¹ means an N-heterocyclic carbene ligand or aligand P(R²)₃ wherein R² means unsubstituted or substituted, straightchain or branched C₁-C₁₄ alkyl, unsubstituted or substituted C₅-C₂₄aryl, or unsubstituted or substituted C₃-C₂₀ cycloalkyl; Z means B; X¹means Cl; and R¹ are identical or different and represent Cl,unsubstituted or substituted, straight chain or branched C₁-C₆ alkyl,C₅-C₆ cycloalkyl, or unsubstituted or substituted phenyl.
 8. The processaccording to claim 5, wherein: M means Ru; X means O or S; D means S, O,PR², or NR² with R² meaning straight chain or branched C₁-C₆ alkyl,C₅-C₆ cycloalkyl, or phenyl; Y means 1,2-ethylene or 1, 2-phenyl; Rmeans phenyl with none or 5 substituents selected from the groupconsisting of F, Cl, Br, and I; L¹ is selected from the group consistingof PPh₃, P(p-Tol)₃, P(o-Tol)₃, PPh(CH₃)₂, P(CF₃)₃, P(p-FC₆H₄)₃,P(P—CF₃C₆H₄)₃, P(C₆H₄—SO₃Na)₃, P(CH₂C₆H₄—SO₃Na)₃, P(isopropyl)₃,P(CHCH₃(CH₂CH₃))₃, P(cyclopentyl)₃, P(cyclohexyl)₃, P(neopentyl)₃,P(neophyl)₃, and N-heterocyclic carbene ligands of the structures(VIII-a) to (VIII-o)

Z means B; X¹ means Cl; and R¹ are Cl.
 9. A process for preparingcompounds, the process comprising subjecting a starting compound to ametathesis reaction or a hydrogenation reaction in the presence of acatalyst consisting of the complex according to claim
 1. 10. The processaccording to claim 9, wherein the process is for preparing a nitrilerubber with a weight average molecular weight M_(w)′, the processcomprising subjecting a starting nitrile rubber having a weight averagemolecular weight M_(w) to a cross-metathesis reaction, wherein theweight average molecular weight of the starting nitrile rubber M_(w) ishigher than the weight average molecular weight M_(w)′ of the nitrilerubber prepared.
 11. The process according to claim 9, wherein theprocess is for preparing a partially or fully hydrogenated nitrilerubber, the process comprising subjecting a starting nitrile rubber to ahydrogenation reaction in the presence of the catalyst to partially orfully hydrogenate the nitrile rubber.
 12. The process according to claim11, wherein the starting nitrile rubber is a copolymer containingrepeating units of at least one conjugated diene and at least oneα,β-unsaturated nitrile monomer, or a terpolymer containing repeatingunits of at least one conjugated diene, at least one α,β unsaturatednitrile monomer, and one or more further copolymerizable monomersselected from α,β-unsaturated monocarboxylic acids, their esters oramides, α,β-unsaturated dicarboxylic acids, their monoesters ordiesters, or their corresponding anhydrides or amides.
 13. A complexaccording to general formula (IV)

wherein M means Ru, Os or Fe; X means O or S; D means S, O, PR², or NR²with R² meaning straight chain or branched C₁-C₁₄ alkyl, C₃-C₈cycloalkyl, preferably C₅- or C₆-C₂₄ aryl; Y means a divalent moiety oran unsubstituted or substituted C₆-C₁₀ arylene group; R meansunsubstituted or substituted C₆-C₁₄ aryl; L¹ means a ligand; Z means B,Al, Ga, or In; R¹ are identical or different and represent F, Cl, Br, I,unsubstituted or substituted, straight chain or branched C₁-C₁₄ alkyl,C₃-C₈ cycloalkyl, unsubstituted or substituted C₆-C₂₄ aryl; and X¹ meansF, Cl, Br, or I.
 14. A process for preparing compounds, the processcomprising subjecting a starting compound to a metathesis reaction or ahydrogenation reaction in the presence of a catalyst consisting of thecomplex according to claim
 13. 15. A transition metal complex accordingto general formula (II)

wherein M means Ru, Os or Fe; X means O or S; D means S, O, NR² or PR²with R² meaning straight chain or branched C₁-C₁₄ alkyl, C₃-C₈cycloalkyl, or C₆-C₂₄ aryl; Y means a divalent moiety or anunsubstituted or substituted C₆-C₁₀ arylene group; R means unsubstitutedor substituted C₆-C₁₄ aryl; L¹ means a ligand.
 16. A process forpreparing the transition metal complex (II) according to claim 15, theprocess comprising: reacting a compound of general formula (VII)

wherein X means O or S; D means S, O, PR², or NR² with R² meaningstraight chain or branched C₁-C₁₄ alkyl, C₃-C₈ cycloalkyl, or C₆-C₂₄aryl; Y means a divalent moiety or an unsubstituted or substitutedC₆-C₁₀ arylene group; and R means unsubstituted or substituted C₆-C₁₄aryl, with either (i) a M-based complex containing at least one L¹ligand of general formula (VIII)M(L¹)₃(H)₂  (VIII) wherein M is Ru, Os or Fe; and L¹ means a ligand; or(ii) a M⁰ complex of general formula (IX)M(L³)_(t)  (IX) wherein t is 2, 3, 4, 5, or 6, and L³ are identical ordifferent and represent coordinated, straight chain or cyclic olefinsand arenes, and a ligand L¹ having the same meanings as given forgeneral formula (VIII).
 17. A process for preparing the transition metalcomplex (II) according to claim 15, the process comprising: reacting acompound of general formula (X)

wherein M means Ru, Os or Fe; R means unsubstituted or substitutedC₆-C₁₄ aryl; L¹ are identical or different and mean a ligand; and X² areidentical or different and represent an anionic ligand with a compoundof general formula (XI)D[(Y—X)⁻K⁺]₂  (XI) wherein X means O or S; D means S, O, PR², or NR²with R² meaning straight chain or branched C₁-C₁₄ alkyl, C₃-C₈cycloalkyl, or C₆-C₂₄ aryl; Y means a divalent moiety or anunsubstituted or substituted C₆-C₁₀ arylene group; and K⁺ means a monocharged cation or any equivalent thereof.